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US4891399A - Thermoplastic resin-based molding composition - Google Patents

Thermoplastic resin-based molding composition Download PDF

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Publication number
US4891399A
US4891399A US07/110,129 US11012987A US4891399A US 4891399 A US4891399 A US 4891399A US 11012987 A US11012987 A US 11012987A US 4891399 A US4891399 A US 4891399A
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United States
Prior art keywords
molding composition
weight
polypropylene
range
amount
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US07/110,129
Inventor
Hideo Ohkawa
Masakuni Chikushi
Hironori Nakamura
Shinji Funayama
Takashi Hashimoto
Takahiro Hirai
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Idemitsu Fine Composites Co Ltd
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CALP Corp
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Priority claimed from JP62156296A external-priority patent/JPS63225657A/en
Priority claimed from JP15935687A external-priority patent/JPH0764983B2/en
Priority claimed from JP62166464A external-priority patent/JPH0764984B2/en
Application filed by CALP Corp filed Critical CALP Corp
Assigned to CALP CORPORATION, 1-277 KANDA-IZUMICHO CHIYODA-KU, TOKYO JAPAN A CORP. OF JAPAN reassignment CALP CORPORATION, 1-277 KANDA-IZUMICHO CHIYODA-KU, TOKYO JAPAN A CORP. OF JAPAN ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CHIKUSHI, MASAKUNI, FUNAYAMA, SHINJI, HASHIMOTO, TAKASHI, HIRAI, TAKAHIRO, NAKAMURA, HIRONORI, OHKAWA, HIDEO
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a thermoplastic resin-based molding composition or, more particularly, to a molding composition based on a thermoplastic resin as the matrix compound with a specific filler and suitable for molding various shaped articles used in a wide variety of applications including, for example, structural parts in electric and electronic instruments, industrial machines and transportation machines such as automobiles as well as furnitures and other household commodities.
  • thermoplastic resins have advantages over metallic materials in respect of their good workability, excellent corrosion resistance, lightness in weight and inexpensiveness so that they are useful as a base material for the manufacture of various shaped articles such as structural parts of instruments and machines as well as furnitures and other household commodities.
  • Thermoplastic resins in general are inferior in the mechanical properties such as tensile strength, impact strength and hardness in comparison with metallic materials and are not quite satisfactory in respect of the heat resistance and dimensional stability.
  • the usually advantageous feature of lightness in weight may in some cases cause a disadvantage to give a trifling impression as commercial goods.
  • thermoplastic resins such as polypropylene, polyethylene, polyamide, poly(ethylene terephthalate), poly(butylene terephthalate) and the like are compounded with a fine powder of a metal such as zinc, copper, iron and the like as a filler to give a resin-based composite molding compound.
  • Shaped articles prepared from such a metal-filled molding compound however, more or less have an unavoidable serious problem of rusting of the metal particles contained in the shaped article to cause poor appearance or degradation in the mechanical properties when the article is prolongedly kept in humid air, water, soil or other corrosive environment.
  • rusting occurs in the molding compound before molding, which is usually in the form of pellets, moreover, drawbacks are sometimes caused in the molding work of such a deteriorated molding compound.
  • the corrosion-resistant coating layer formed on the surface of a shaped article has a problem of inherently low durability because the coating layer gradually falls off the surface with time.
  • the productivity of shaped articles must decrease because the process is complicated for forming such a protective surface layer.
  • the method of forming a skin layer is particularly defective when the shaped article has an irregular configuration or non-uniform wall thickness due to the extreme difficulty in obtaining a skin layer of uniform thickness.
  • the productivity of course cannot be high enough.
  • the method of wrapping with a plastic film also suffers low productivity due to the complicated and troublesome process if not to mention the limited applicability of the method.
  • conventional metallic filler-loaded composite molding compounds have problems in the moldability of the compound and stability of the shaped articles therefrom, especially, when the molding compound has a density in excess of 1.5 g/cm 3 or, in particular, 2.0 g/cm 3 .
  • the moldability of such a molding compound is poor so that the appearance of the articles shaped therefrom is sometimes not quite acceptable.
  • the shaped articles of such a molding compound usually have relatively low mechanical strengths or, in particular, impact strength and exhibit a large molding shrinkage sometimes with different ratios of shrinkage between directions. Therefore, it is a rather difficult matter to obtain a satisfactory shaped article of high density with good dimensional stability exhibiting no warping distortion from such a metallic filler-loaded molding compound.
  • the molding compound is also not quite satisfactory as a moldable electroconductive material because sufficiently high electroconductivity can hardly be obtained or the reproducibility of the conductivity, if obtained, is usually low.
  • An object of the present invention therefore is to provide a novel thermoplastic resin-based molding composition loaded with a metallic filler free from the above described problems and disadvantages in the conventional metallic filler-loaded molding compounds.
  • the molding composition of the present invention should have good moldability and be capable of giving shaped articles having good appearance and high mechanical properties as well as dimensional stability, electroconductivity and resistance against rusting and also suitable for secondary machining such as cutting, grinding and lathing using standard machine tools.
  • thermoplastic resin with a specific amount of a metallic filler after a surface treatment of the particles with a specific amount of a compound belonging to the class of so-called water repellent agents, optionally, with further admixture of a small amount of a low-molecular weight oxidized polypropylene.
  • thermoplastic resin-based molding composition of the present invention comprises:
  • thermoplastic polymer from 2 to 70 parts by weight of a thermoplastic polymer as the matrix phase
  • the molding composition is additionally admixed with (C) a low-molecular weight oxidized polypropylene, the composition comprises:
  • thermoplastic polymer from 2 to 70 parts by weight of a thermoplastic polymer
  • (C) a low-molecular weight oxidized polypropylene in an amount in the range from 0.1 to 2% by weight based on the total amount of the components (A) and (B).
  • the metallic filler as the component (B) in the above given formulations should be a combination of a particulate metallic filler having an average particle diameter, for example, in the range from 0.1 to 20 ⁇ m and a fibrous metallic filler having a fiber diameter in the range from 0.03 to 60 ⁇ m or, preferably, from 0.1 ⁇ 20 ⁇ m and an aspect ratio in the range from 50 to 2500 in a weight ratio not exceeding 1:1 or, preferably, in the range from 1:1 to 30:1.
  • the component (A) to form the matrix phase of the inventive molding composition is a thermoplastic polymer which is not limited to a particular type but may be selected from various kinds of thermoplastic resins and elastomers either singly or as a combination of two kinds or more according to need.
  • thermoplastic resins include polyolefin resins, poly(vinyl chloride) resins, polyamide resins, polyimide resins, polyester resins, polyacetal resins, polycarbonate resins, poly(aromatic ether or thioether) resins, poly(aromatic ester) resins, polysulfone resins, polystyrene resins, acrylic resins, fluorocarbon resins and the like.
  • the polyolefin resins include homopolymers and copolymers of ⁇ -olefins such as ethylene, propylene, butene-1, 1-methyl-butene-1, 3-methylpentene-1, 4-methylpentene-1 and the like as well as copolymers of these monomers as the principal ingredient with another monomer of a different type.
  • polystyrene resins are high-density, medium-density and low-density polyethylenes, straight-chained polyethylenes, super-high molecular polyethylenes, copolymers of ethylene and vinyl acetate and other ethylene-based polymers, atactic, syndiotactic and isotactic polypropylenes, block and random copolymers of propylene and ethylene and other propylene-based polymers, poly(4-methylpentene-1) and the like.
  • these polyolefins may be modified by the graft polymerization of a polar vinylic monomer such as ⁇ , ⁇ -unsaturated carboxylic acids and esters thereof exemplified by acrylic acid, esters of acrylic acid, methacrylic acid, esters of methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid and the like or an unsaturated epoxide exemplified by glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether and the like.
  • a polar vinylic monomer such as ⁇ , ⁇ -unsaturated carboxylic acids and esters thereof exemplified by acrylic acid, esters of acrylic acid, methacrylic acid, esters of methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid and the
  • the poly(vinyl chloride) resins include homopolymeric poly(vinyl chloride) resins and copolymeric resins of vinyl chloride with another monomer copolymerizable therewith.
  • the copolymeric resins are exemplified by the copolymers of vinyl chloride and an acrylic acid ester, copolymers of vinyl chloride and a methacrylic acid ester, copolymers of vinyl chloride and ethylene, copolymers of vinyl chloride and propylene, copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride and vinylidene chloride and the like.
  • These poly(vinyl chloride) resins may be post-chlorinated to have an increased content of chlorine.
  • the polyamide resins include 6-nylon, 12-nylon and the like obtained by the ring-opening polymerization of an aliphatic cyclic lactam, 6,6-nylon, 6,10-nylon, 6,12-nylon and the like obtained by the condensation-polymerization of an aliphatic diamine and an aliphatic dicarboxylic acid, condensation-polymerization of m-xylene and adipic acid and the like obtained by the condensation-polymerization of an aromatic diamine and an aliphatic dicarboxylic acid, condensation-polymerizates of p-phenylene diamine and terephthalic acid or m-phenylene diamine and isophthalic acid and the like obtained by the condensation-polymerization of an aromatic diamine and an aromatic dicarboxylic acid, 11-nylon and the like obtained by the condensation-polymerization of an amino acid, and so on.
  • the polyimide resins include polyimides and polyamideimides.
  • Exemplary of the polyimides are these obtained from the combinations of pyromellitic anhydride and diamino diphenyl ether, 3,4,3',4'-benzophenone tetracarboxylic acid anhydride and diamino diphenyl ether, bismaleimide and diamino diphenyl methane and the like.
  • Exemplary of the polyamideimides are those obtained from the combination of trimellitic anhydride and diamino diphenyl ether and the like.
  • the polyester resins include those obtained by the condensation-polymerization of an aromatic dicarboxylic acid and an alkylene glycol exemplified by poly (ethylene terephthalates), poly (methylene terephthalates) and the like.
  • the polyacetal resins are exemplified by the homopolymeric polyoxymethylenes and copolymers of formaldehyde and ethylene oxide obtained from trioxane and ethylene oxide.
  • polycarbonate resins are the 4,4'-dihydroxy diallyl alkane-based polycarbonates and the bisphenol A-based polycarbonates prepared by the phosgene method, in which bisphenol A and phosgene A and phosgene are reacted, or the ester interchange method, in which bisphenol A and a diester of carbonic acid such as diphenyl carbonate are reacted.
  • Usable polycarbonate resins include those modified or flame-retardant bisphenol A-based polycarbonates obtained by partially replacing the bisphenol A in the above mentioned preparation of unmodified polycarbonates with 2,2-bis (4-hydroxy-3,5-dimethyl phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromo phenyl) propane and the like.
  • the poly(aromatic ether or thioether) resins have ether linkages or thioether linkages in the polymeric molecular chain and are exemplified by polyphenylene oxides, styrene-grafted polyphenylene oxides, polyphenylene sulfides and the like.
  • the poly(aromatic ester) resins are exemplified by polyoxybenzoyls obtained by the condensation-polymerization of 4-hydroxy benzoic acid and polyarylates obtained by the condensation-polymerization of bisphenol A and an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid.
  • the polysulfone resins have sulfone linkages in the polymeric molecular chain and are exemplified by polysulfones obtained by the condensation-polymerization of bisphenol A 4,4'-dichlorodiphenyl sulfone, polyether sulfones having a structure in which phenylene groups are bonded together at the 1,4-positions through ether linkages and sulfone linkages and polyaryl sulfones having a structure in which diphenylene groups and diphenylene ether groups are alternately bonded together through sulfone linkages.
  • the polystyrene resins include homopolymers of styrene and ⁇ -methyl styrene and copolymers thereof as well as copolymers of them as the principal ingredient with another monomer copolymerizable therewith.
  • polystyrene resins are general-purpose polystyrenes, high-impact polystyrenes, heat-resistant polystyrenes, polymers of ⁇ -methyl styrene, copolymers of acrylonitrile, butadiene and styrene (ABS), copolymers of acrylonitrile and styrene (AS), copolymers of acrylonitrile, chlorinated polyethylene and styrene (ACS), copolymers of acrylonitrile, ethylenepropylene rubber and styrene (AES), copolymers of acrylic rubber, acrylonitrile and styrene and the like.
  • the acrylic resins include polymers of acrylic acid esters and methacrylic acid esters exemplified by methyl, ethyl, n-propyl, isopropyl and butyl esters of acrylic acid and methacrylic acid. Particularly preferable among them are poly(methyl methacrylate) resins from the standpoint of practically using the inventive molding composition as an industrial material.
  • the fluorocarbon resins include homopolymers of tetrafluoro ethylene, hexafluoro propylene, vinylidene fluoride, vinyl fluoride and the like and copolymers thereof as well as copolymers of these fluorinated monomers as the principal ingredient with another monomer copolymerizable therewith.
  • fluorocarbon resin examples include poly(tetrafluoroethylenes), poly(vinylidene fluorides), poly(vinyl fluorides), copolymers of tetrafluoroethylene and ethylene, copolymers of tetrafluoroethylene and vinylidene fluoride, copolymers of hexafluoropropylene and vinylidene fluoride, copolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride and the like.
  • the elastomeric polymers suitable as the component (A) include natural rubber and various kinds of synthetic rubbers exemplified by polybutadiene rubbers (BR), copolymeric rubbers of styrene and butadiene (SBR), copolymeric rubbers of acrylonitrile and butadiene (NBR), copolymeric rubbers of styrene, butadiene and acrylonitrile, polychloroprene rubbers (CR) and other butadiene-based rubbers, polyisoprene rubbers or synthetic natural rubbers, copolymeric rubbers of isobutylene and isoprene or so-called butyl rubbers (IIR), copolymeric rubbers of acrylonitrile and isoprene, polyisobutylene rubbers, copolymeric rubbers of ethylene and propylene, copolymeric rubbers of ethylene and vinyl acetate, chlorinated polyethylenes, chlorosulfonated polyethylenes, ure
  • polymers can be used either singly or as a mixture of two kinds or more according to need as the component (A) to form the matrix phase of the inventive molding composition.
  • Particularly preferable among them are polyamide resins such as 6-nylon, 6,6-nylon, 12-nylon and the like, polypropylenes and poly(butylene terephthalates).
  • the components (B) to form the disperse phase in the inventive molding composition is a metallic filler usually in a particulate form.
  • Metals of which the powder as the metallic filler is prepared include zinc, copper, iron, lead, aluminum, nickel, chromium, titanium, manganese, tin, platinum, tungsten, gold, magnesium, cobalt, strontium and the like as well as alloys of these metallic elements such as stainless steel, solder alloys, brass, bronze and the like, of which zinc is particularly preferred.
  • Zinc oxide also can be used.
  • Certain ceramic materials obtained in a powdery form can be used as the filler including silicon carbide, silicon nitride, zirconia, aluminum nitride, titanium carbide and the like.
  • the metallic filler in a particulate form as the component (B) should have an average particle diameter in the range from 0.2 to 2.0 ⁇ m or, preferably, in the range from 0.4 to 10 ⁇ m.
  • the molding composition compounded with the filler may be poor in the moldability.
  • the molding composition compounded with the filler cannot give a shaped article having a sufficiently high impact strength and free from the drawbacks of warping distortion after molding.
  • Suitable fibrous fillers include inorganic fibers such as glass fibers, carbon fibers, magnesium sulfate fibers and the like, fibers and whiskers of a metal such as stainless steel, brass, aluminum, nickel and the like, whiskers of ceramics such as potassium titanate, silicon carbide and the like, and organic fibers such as aromatic polyamide fibers, cellulosic fibers, nylon fibers, polyester fibers, polypropylene fibers and the like.
  • glass fibers Preferable among them are glass fibers, carbon fibers, stainless steel fibers, brass fibers, potassium titanate whiskers, aromatic polyamide fibers and the like. Glass fibers are particularly preferred. These fibrous fibers can be used either singly or as a combination of two kinds or more accordingly to need.
  • the fibers of the fibrous filler should have a fiber diameter in the range from 0.03 to 60 ⁇ m or, preferably, from 0.1 ⁇ 20 ⁇ m and an aspect ratio in the range from 50 to 2500 or, preferably, from 100 to 2000.
  • the aspect ratio of the fibers is to small, desired improvement in the impact strength of the shaped article cannot be achieved as desired.
  • the shaped articles of the molding composition may be subject to an increased molding shrinkage and drawbacks of warping distortion after molding so that the molding composition cannot be used industrially due to the poor dimensional stability of the shaped articles therefrom.
  • the weight ratio of them should not exceed 1:1 although no substantial improvement can be obtained in the impact strength of the shaped articles molded of the composition when the amount of the fibrous filler is too small.
  • the weight ratio of the particulate to fibrous fillers should be in the range from 1:1 to 30:1 or, preferably, from 2:1 to 20:1.
  • Suitable water repellent agents include silane-based coupling agents, titanate-based coupling agents, silicone fluids, higher fatty acids, higher alcohols, waxes and the like, of which silane-based coupling agents, titanate-based coupling agents and silicone fluids are preferred. These water repellent agents can be used either singly or as a combination of two kinds or more according to need.
  • silane-based coupling agent is not particularly limitative, and any of known ones can be used.
  • suitable silane-based coupling agents are triethoxy silane, vinyl tris ( ⁇ -methoxyethoxy) silane, 3-methacryloxypropyl trimethoxy silane, 3-glycdyloxypropyl trimethoxy silane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxy silane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxy silane, 3-aminopropyl triethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane, 3-mercaptopropyl trimethoxy silane, 3-chloropropyl trimethoxy silane and the like, of which 3-aminopropyl triethoxy silane,
  • titanate-based coupling agents are isopropyl triisostearoyl titanate, isopropyl tri(dodecylbenzene sulfonyl) titanate, isopropyl tris(dioctyl pyrophosphato) titanate, tetraisopropyl bis(dioctylphosphito) titanate, tetraoctyl bis(ditridecyl phosphito) titanate, tetra(2,2-diallyloxy methyl-1-butyl) bis(di-tridecyl phosphito) titanate, bis(dioctyl pyrophosphato) oxyacetate titanate bis(dioctyl pyrophosphato) ethylene titanate, isopropyl trioctanoyl titanate
  • suitable silicone fluids include dimethyl silicone fluids, methyl phenyl silicone fluids, polyether-modified silicone fluids, alkyl-modified silicone fluids, methyl hydrogen polysiloxane fluids and the like, of which dimethyl silicone fluids and methyl hydrogen polysiloxane fluids are preferred.
  • dimethyl silicone fluids methyl hydrogen polysiloxane fluids and 3-aminopropyl triethoxy silane are particularly preferable as the surface treatment agent of the filler as the component (B) in the inventive molding composition.
  • the procedure for the surface treatment of the component (B) with the water repellent agent is not particularly limitative according to any known method conventionally undertaken for the surface treatment of a powdery material.
  • a preferable method in respect of the versatility and controllability of the temperature and mixing velocity in the treatment is to use a Henschel mixer in which the water repellent agent is sprayed on to the filler under agitation and thoroughly mixed together.
  • the water repellent agent in this surface treatment of the filler as the component (B) should be used in an amount in the range from 0.01 to 5% by weight or, preferably, from 0.05 to 3% by weight or, more preferably, from 0.1 to 2% by weight based on the amount of the filler as the component (B) before the surface treatment.
  • the amount of the water repellent agent is too small, no sufficient coupling effect can be exhibited between the surface of the filler and the matrix phase so that the resultant molding composition would be poor in the moldability.
  • the fillers thus surface-treated or coated with the water repellent agent as the component (B) can be used either singly or as a combination of two kinds or more according to need.
  • the compounding amount of the component (B) in the inventive molding composition should be in the range from 30 to 98 parts by weight or, preferably, from 50 to 97 parts by weight or, more preferably, from 60 to 95 parts by weight per 100 parts by weight of the total amount of the components (A) and (B).
  • the inventive molding composition can be further admixed with a low-molecular weight oxidized polypropylene as the component (C) in an amount in the range from 0.1 to 2% by weight based on the total amount of the polymeric matrix phase as the component (A) and the filler after the surface treatment as the component (B).
  • the low-molecular weight oxidized polypropylene is prepared by the oxidative degradation of, for example, an isotactic polypropylene as a solid or melt or in the form of a solution with an oxidizing agent such as peroxides. Carboxyl groups and other types of oxygen-containing groups are introduced into the molecular structure of the polypropylene by this oxidizing reaction.
  • the low-molecular weight oxidized polypropylene has increased miscibility with thermoplastic resins having polarity such as polyamides in comparison with non-oxidized low-molecular weight polypropylenes. It is preferable to use a low-molecular weight oxidized polypropylene having an average molecular weight in the range from 1500 to 20000.
  • the molding composition is imparted with improved moldability and capable of giving shaped articles having improved mechanical strengths and electric conductivity.
  • a modifier such as a modified polyolefin which serves to increase the affinity between the polymeric matrix as the component (A) and the surface of the filler as the component (B).
  • Suitable polyolefin-based modifiers include, for example, polyethylene and polypropylene modified by graft-polymerization of 0.05 to 20% by weight of a monomer exemplified by unsaturated organic acids and derivatives thereof such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and other organic acids, maleic anhydride, itaconic anhydride, citraconic anhydride and other anhydrides of unsaturated organic acids, methyl acrylate, monomethyl maleate and other esters of unsaturated organic acids, acrylamide, fumaric acid monoamide and other amides of unsaturated organic acids, itaconic acid imide and other imides of unsaturated organic acids, and so on.
  • unsaturated organic acids and derivatives thereof such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and other organic acids, maleic anhydride, itaconic anhydride, citraconic anhydride and other anhydrides of unsaturated organic acids, methyl acryl
  • the modification reaction of the polyolefin by the polymerization of these monomers can be accelerated by an organic peroxide such as benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide and the like.
  • organic peroxide such as benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide and the like.
  • Usable modifiers in addition to the above described ones include ethylene- or propylene-based polymers modified by graft polymerization of an unsaturated epoxide such as glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, ally glycidyl ether and the like carried out optionally with admixture of a liquid rubber such as a polybutadiene hydroxylated at the molecular chain ends.
  • an unsaturated epoxide such as glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, ally glycidyl ether and the like carried out optionally with admixture of a liquid rubber such as a polybutadiene hydroxylated at the molecular chain ends.
  • the amount of these modifiers added to the inventive molding composition should usually be in the range from 1 to 10% by weight based on the total amount of the components (A) and (B).
  • the amount thereof is too small, the desired improvement by the addition of the modifier cannot be fully exhibited as a matter of course.
  • phase separation may sometimes take place in the shaped article of the composition to greatly decrease the mechanical strengths.
  • the molding composition of the invention is further admixed with various kinds of inorganic and organic fillers though in a limited amount not to substantially affect the desirable properties of the composition or the shaped article prepared therefrom.
  • Such an optional filler may be powdery, granular or fibrous.
  • Inorganic fillers suitable for the above mentioned optional addition are exemplified by oxides such as silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice, pumice ballons and the like, hydroxides such as aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate and the like, carbonates such as calcium carbonate, magnesium carbonate, dolomite, dawsonite and the like, sulfates and sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite and the like, silicates such as talc, clay, mica, asbestos, glass balloons, glass beads, montmorillonite, bentonite and the like, carbonaceous filler such as carbon black, graphite powder, carbon balloons and the like, molybdenum sulfide, zinc borate, barium metaborate, calcium borate, sodium borate and the like. These inorganic filler can be used
  • Organic fillers suitable for the above mentioned optional addition are exemplified by non-fibrous ones such as rice hulls, wood flour, fragments of paper and cellophane and the like. These organic filler also can be used either singly or as a combination of two kinds or more according to need. It is of course optional that inorganic and organic fillers are used in combination.
  • the molding composition of the invention can be admixed with various kinds of additives conventionally compounded in resin-based molding compositions including, for example, lubricants, coloring agents, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardant agents, plasticizers, blowing agents and the like according to the intended application of the articles shaped from the molding composition.
  • additives conventionally compounded in resin-based molding compositions including, for example, lubricants, coloring agents, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardant agents, plasticizers, blowing agents and the like according to the intended application of the articles shaped from the molding composition.
  • the molding composition of the present invention can be prepared by uniformly blending and compounding the components (A) and (B), optionally, together with the component (C) and above described optional additives in a conventional procedure of kneading in a molten condition by using a suitable blending machine such as Henschel mixers, single-or double-screw extruder machines, Banbury mixers, roller mixers and the like, of which Henschel mixers, extruder machines and Bunbury mixers are preferred.
  • a suitable blending machine such as Henschel mixers, single-or double-screw extruder machines, Banbury mixers, roller mixers and the like, of which Henschel mixers, extruder machines and Bunbury mixers are preferred.
  • the molding composition of the present invention can be shaped into articles by any conventional molding method such as injection molding, extrusion molding, compression molding and the like without particular limitations by virtue of the good moldability.
  • the composition can give not only shaped articles having complicated configuration as molded but also shaped articles suitable for secondary work-ing to meet various applications by adequately modifying the blending ratio of the components.
  • the application fields of the shaped articles of the inventive molding composition include structural and functional parts in electric and electronic instruments, machines in general, automobiles and the like, furnitures, household commodities and so on.
  • shaped articles are, for example, all kinds of rotary members for power transmission such as flywheels, gears, pulleys, cams, motors and the like, housing, chassis, turn tables and the like of record players, cassette tape recorders, speaker boxers, etc., sound insulating and shielding materials, vibra-tion dumping materials, shielding materials for electro-magnetic waves, furnitures, kitchenwares, office supplies, toys, fishing implements and so on.
  • thermoplastic resin-based molding composition of the present invention is prepared by compounding a thermoplastic polymer as the matrix phase with a metallic filler after a surface treatment with a water repellent agent so that the filler particles dispersed in the polymeric matrix are highly resistant against rusting along with greatly improved affinity between the surface of the filler particles and the matrix polymer.
  • the inventive molding composition has good moldability and is capable of giving shaped articles having outstandingly good outer appearance, excellent mechanical properties, high dimensional stability without warping distortion and stable electric conductivity.
  • the inventive molding composition can be shaped into articles having large dimensions or a complicated configuration and the shaped articles have good secondary workability suitable for machining with standard machine tools such as cutting, grinding, lathing and the like.
  • present invention provides a material having excellent moldability into shaped articles and machinability of the shaped articles in combination.
  • Such a combination of moldability and machinability is the very great advantage of the inventive molding composition never obtained in any of conventional resin-based molding composition and metals.
  • the polymeric materials used as the polymeric matrix of the molding compositions include the commercially available products listed below, each of which is referred to hereinbelow with the abridged symbols of the name preceding the name of the polymeric material.
  • 6-PA 6-nylon, LM-102, a product by Kanegafuchi Chemical Industry Co.
  • PP polypropylene, J2000G, a product by Idemitsu Petro-chemical Co.
  • PBT poly(butylene terephthalate), 5010, a product by Mitsubishi Chemical Industries Co.
  • PET poly(ethylene terephthalate), MA 2101, a product by Unitika Co.
  • POM polyacetal, 3010, a product by Asahi Chemical Industry Co.
  • PE polyethylene, 110J, a product by Idemitsu Petro-chemical Co. having a melt index of 14 g/10 minutes
  • ABS copolymeric resin of acrylonitrile, butadiene and styrene, JSR-35, a product by Japan Synthetic Rubber Co.
  • PC polycarbonate, N-2500, a product by Idemitsu Petro-chemical Co.
  • PVC poly(vinyl chloride), JZ-102F, a product by Shin-Etsu Polymer Co.
  • PMMA poly(methyl methacrylate), 50N, a product by Asahi Chemical Industry Co.
  • PPO poly(phenylene oxide), 731J, product by Engineering Plastics Co.
  • PSO polysulfone, P-1700, a product by Nissan Chemical Co.
  • PI polyimide, SP-1, a product by DuPont Far East Co.
  • SBR styrene-butadiene rubber
  • JSR-1500 a product by Japan Synthetic Rubber Co.
  • EPR ethylene-propylene copolymeric rubber, EP-07P, a product by Japan Synthetic Rubber Co.
  • EVA ethylene-vinyl acetate copolymer rubber
  • Evatate D-3021 a product by Sumitomo Chemical Co.
  • (23) POE polyolefin-based elastomer, TPE-1500, a product by Sumitomo Chemical Co.
  • ZN zinc powder having an average particle diameter of about 3 ⁇ m, a product by Sakai Chemical Co.
  • ZnO zinc oxide having an average particle diameter of about 3 ⁇ m, a product by Sakai Chemical CO.
  • (3) CU copper powder having an average particle diameter of about 5 ⁇ m, a product by Fukuda Kinzoku Hakufun Kogyo Co.
  • ⁇ -FE iron powder having an average particle diameter of about 0.5 ⁇ m, a product by Dowa Teppun Kogyo Co.
  • ⁇ -Fe 2 O 3 iron oxide powder having an average particle diameter of about 0.5 ⁇ m, a product by Dowa Teppun Kogyo Co.
  • Ni nickel powder having an average particle diameter of about 3 ⁇ m
  • Pb lead powder having an average particle diameter of 10 ⁇ m
  • Al aluminum powder having an average particle diameter of about 10 ⁇ m
  • NF nickel fibers having a diameter of 10 ⁇ m and fiber length of 8 mm
  • PT whiskers of potassium titanate having a diameter of 0.3 ⁇ m and length of 15 ⁇ m
  • ZrO 2 zirconia powder having an average particle diameter of about 0.5 ⁇ m
  • E isopropyl triisostearoyl titanate, a product by Ajinomoto Co.
  • G finely divided silica powder having an average particle diameter of about 12 ⁇ m, a product by Nippon Aerosil Co.
  • H finely divided silica powder having an average particle diameter of about 7 ⁇ m, a product by Nippon Aerosil Co.
  • a 0.3 part by weight of 3-aminopropyl triethoxy silane was sprayed to 100 parts by weight of a zinc powder having an average particle diameter of 3 ⁇ m contained in a Henschel mixer of 20 liter capacity and the mixer was run for 5 minutes at a velocity of 1000 rpm to mix them together at a temperature of 60° to 100° C. to prepare a surface-coated zinc powder. Thereafter, a 6-PA resin in an amount of 50 % by weight based on the surface-coated zinc powder was added to the mixer and melted and mixed together by running the mixer for 15 minutes at a velocity of 2000 rpm and at a temperature of 200° to 300° C.
  • a composite molding resin composition with further admixture of 0.3% by weight of an antioxidant (Irganox 1010, a product by Ciba Geigy Co.), 0.3% by weight of calcium stearate as a lubricant (a product by Nippon Yushi Co.) and 1.0% by weight of carbon black (DL-600, a product by Lion Akzo Co.), each amount being based on the total amount of the 6-PA resin and the surface-coated zinc powder.
  • an antioxidant Irganox 1010, a product by Ciba Geigy Co.
  • calcium stearate as a lubricant
  • carbon black DL-600, a product by Lion Akzo Co.
  • the thus obtained molding composition was pelletized by using a single-screw extruder machine (Model NVC-50, manufactured by Nakatani Machinery Co.) operated at a temperature of 200° to 300° C. with a rate of extrusion of 30 kg/hour and the pellets were shaped into test plates by injection molding using an injection molding machine (Model FS-160S; manufactured by Nissei Resin Industry Co.) at a temperature of 200° to 300° C.
  • Model FS-160S manufactured by Nissei Resin Industry Co.
  • test plates were subjected to the evaluation of various properties including the following items each according to the procedure described below. The results are shown in Table 1.
  • test plate of 75 mm by 75 mm wide and 3.2 mm thick was put into a bag made of a polyethylene film of 40 ⁇ m thickness and, after sealing of the opening by welding, the bag was heated for 100 hours or 300 hours in an atmosphere of 95% relative humidity at 60° C.
  • the test plate taken out of the bag was inspected for the surface condition with naked eyes or by using a magnifying lens of 25 magnification to give the results in four ratings of A, B, C and D according to the following criteria.
  • a box having outer dimensions of 150 mm by 80 mm by 80 mm with a wall thickness of 5 mm was shaped from the molding composition by injection molding using the same injection molding machine as used in the preparation of the test plates above to determine the critical impregnation pressure or minimum impregnation pressure for short shot in kg/cm 2 .
  • the thus molded boxes were visually inspected for the outer appearance and the results were expressed in three ratings of A, B and C according to the following criteria.
  • Measurement was performed according to JIS C 1302 by using an automatic insulation-resistance tester (Model F-535F, manufactured by Fuso Electric Co.) with a voltage impression of 500 volts DC to give the total resistance in megaohm.
  • Model F-535F manufactured by Fuso Electric Co.
  • Example 1 The experimental procedure in each of these Examples and Comparative Examples was substantially the same as in Example 1 using the same zinc powder as the filler expecting replacement of the 6-PA resin as the matrix polymer and the 3-aminopropyl triethoxy silane as the water repellent agent each with the material shown in Table 1 in an amount also indicated in the same table.
  • the amounts of the filler and the matrix polymer given in parts by weight are given per 100 parts by weight of the total amount of the filler after the surface treatment and the matrix polymer and the amount of the water repellent agent given in % by weight is based on the amount of the filler before the surface treatment.
  • the molding compositions prepared in Comparative Examples 2 and 4 were disadvantageous in respect of the low productivity in pelletization due to slipping.
  • Table 1 also shows the results of the evaluation of the products carried out in the same manner as in Example 1.
  • the zinc powder as the filler and the finely divided silica powder as the water repellent agent were dry-blended in the Henschel mixer operated at a velocity of 1000 rpm for 5 minutes at a temperature of 60° to 100° C. before the addition of the 6-PA resin.
  • Example 2 shows the formulation of the molding compositions and the results of evaluation undertaken in the same manner as in Example 1. Examples 104 to 107 and Comparative Examples 14 and 15.
  • a molding resin composition was prepared by first blending, in a Henschel mixer of 20 liter capacity, 15 parts by weight of a 6-PA resin, 85 parts by weight of a ZnO powder having a varied average particle diameter shown in Table 3 below, 0.5 part by weight of a low-molecular oxidized polypropylene having an average molecular weight of 3500 and 0.3 part by weight of an aminosilane-based coupling agent and then kneading the blend thoroughly at 220° to 350° C. in a double-screw kneading machine (Model NAS-50, manufactured by Nakatani Machinery Co.).
  • the thus prepared molding resin composition were each shaped by injection molding into test plates at 220° to 350° C. using the same injection molding machine as used in Example 1.
  • the molding compositions were evaluated by measuring the minimum molding pressure in the injection molding of the composition and the mechanical and electrical properties of the test plates in the following manner. The results are shown in Table 3.
  • Molding pressure a box having dimensions of 90 mm by 150 mm by 70 mm with a wall thickness of 5 mm and a pin gate of 1 mm diameter was shaped by injection molding under the above mentioned conditions to determine the minimum pressure for impregnation in kg/cm 2 G.
  • the low-molecular oxidized polypropylene was a commercial product (Biscol TS-200, a product by Sanyo Kasei Co.) and the aminosilane-based coupling agent was aminopropyl triethoxy silane.
  • the formulation and experimental procedure were substantially the same as in the preceding examples except that the amounts of the 6-PA resin and ZnO filler were 15 parts by weight and 85 parts by weight, respectively, in each of these Examples and Comparative Examples and the amount of the low-molecular oxidized polypropylene, referred to as the component (C) hereinbelow, was varied as indicated in Table 5 below, which also shows the results of evaluation of the molding resin compositions carried out in the same manner as in the preceding examples.
  • reaction mixture was poured into a large volume of acetone and the precipitates formed in acetone were collected by filtration with suction and dried at 70° C. for 50 hours to give a white powder.
  • This powder was subjected to extraction with acetone in a Soxhlet extractor for 16 hours to give a modified polypropylene as the product by removing unreacted polybutadiene and maleic anhydride.
  • a Henschel mixer was charged with 10 parts by weight of one of the fibrous fillers indicated in Table 11, 70 parts by weight of a zinc powder having an average particle diameter of about 3 ⁇ m and 0.5 part by weight of a dimethyl silicone fluid and operated at a velocity of 1000 rpm for 5 minutes at a temperature of 60° to 100° C. to coat the surface of the fibers and zinc particles with the silicone fluid. Thereafter, 20 parts by weight of a 6-PA resin were introduced into the mixer and thoroughly blended together. The thus obtained blend was further kneaded at 220° to 350° C. in a double-screw extruder machine to give a molding resin composition which was then shaped into test plates at 220° to 350° C. by injection molding using the same injection machine as used in Example 1. The molding resin composition were evaluated for the moldability of the composition, mechanical properties of the test plates, molding shrinkage of the molded articles and warping distortion of the molded articles in the following manner.
  • a box having dimension of 90 mm by 70 mm with a wall thickness of 5 mm and a pin gate of 1 mm diameter was shaped from the molding composition by injection molding using an injection molding machine (Model IS-125, manufactured by Toshiba Machines Co.) operated under the standard conditions of a cylinder temperature of 200° to 300° C., temperature of metal mold of 75° to 100° C., injection pressure of 60 kg/cm 2 and shot time of 20 seconds and the moldability of the molding composition was evaluated according to the following criteria in three ratings in terms of the reproducibility of the box configuration by the injection molding and the injection pressure.
  • an injection molding machine Model IS-125, manufactured by Toshiba Machines Co.
  • Tensile strength was determined according to ASTM D-638, Izod impact value was determined according to ASTM D-256 and flexural strength and elastic modules by bending were determined according to ASTM D-790.
  • a circular disc of 45 mm diameter and 2 mm thickness was shaped by injection molding under the same conditions as above and warping of the disc was evaluated by the height ⁇ of the highest point when the disc was placed on a horizontal plane.
  • the results were given in three ratings of A, B, C according to the following criteria.
  • Table 11 given below shows the formulation of the molding resin compositions and the results of the evaluation thereof performed in the above described manner.
  • the kinds of the fibrous fillers are indicated with the symbols of GF, SF, BF, PT, CF, SCF and APAF for glass fibers, stainless steel fibers, brass fibers, whiskers of potassium titanate, carbon fibers, silicone carbide fibers and aromatic polyamide fibers, respectively.
  • each of the molding resin composition was compounded from 20 parts by weight of the 6-PA resin, a varied amount as indicated in Table 12 below of a zinc powder having an average particle diameter of about 3 ⁇ m and a varied amount of a fibrous filler, i.e. glass fibers (GF), stainless steel fibers (SF), potassium titanate whiskers (PT) or carbon fibers (CF), as indicated in Table 12.
  • GF glass fibers
  • SF stainless steel fibers
  • PT potassium titanate whiskers
  • CF carbon fibers
  • thermoplastic resin composition were each compounded from 10 parts by weight of glass fibers having an aspect ratio of 231, 70 parts by weight of zinc powder having an average particle diameter of about 3 ⁇ m and 20 parts by weight of one kind or a combination of two kinds of the thermoplastic resins indicated in Table 14 below, which also shows the results of the evaluation of the molding composition.
  • two kinds of the thermoplastic resins were used, they were taken in equal amounts.
  • Example 145 to 172 The experimental procedure in each of these Examples was substantially the same as in Examples 145 to 172 except that the molding composition were each compounded from 10 parts by weight of glass fibers having an aspect ratio of 231 as a fibrous filler, a varied amount indicated in Table 15 below of a powder of zinc (Examples 224 to 233) or zinc oxide (Examples 234 to 243) each having an average particle diameter of about 3 ⁇ m as a particulate filler and a varied amount of a thermoplastic resin indicated in Table 15, which also shows the results of the evaluation of the molding compositions.
  • Table 15 a powder of zinc (Examples 224 to 233) or zinc oxide (Examples 234 to 243) each having an average particle diameter of about 3 ⁇ m as a particulate filler and a varied amount of a thermoplastic resin indicated in Table 15, which also shows the results of the evaluation of the molding compositions.
  • the experimental procedure in each of these Examples was substantially the same as in Examples 145 to 172 except that the molding resin compositions were each compounded from 10 parts by weight of glass fibers having an aspect ratio of 231 ,70 parts by weight of a zinc powder having an average particle diameter of about 3 ⁇ m and 20 parts by weight of a thermoplastic resin indicated in Table 16 below without or with further admixture of 2 parts by weight of the modified polypropylene resin prepared in Preparation Example 1 as a modifier.
  • the fibrous and particulate fillers were used after a surface treatment with 0.5 part by weight of a dimethyl silicone fluid as the water repellent agent. Table 16 below also shows the results of the evaluation of the molding compositions.

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Abstract

The thermoplastic polymeric molding composition of the invention has good moldability in shaping by injection molding, extrusion molding and compression molding and capable of giving shaped articles having good machinability in mechanical working such as cutting, grinding and latching. The composition is compounded from 2 to 70 parts by weight of a thermoplastic polymer such as a polyamide resin and from 98 to 30 parts by weight of a metallic filler such as zinc powder and zinc oxide powder having a surface coated with a water repellent agent such as silane coupling agents, titanate coupling agents and silicone fluids in a specified amount. A part of the above mentioned particulate filler may optionally be replaced with a fibrous filler such as glass fibers and carbon fibers so that the shaped articles of the molding composition may be imparted with increased impact strength.

Description

BACKGROUND OF THE INVENTION
The present invention relates to a thermoplastic resin-based molding composition or, more particularly, to a molding composition based on a thermoplastic resin as the matrix compound with a specific filler and suitable for molding various shaped articles used in a wide variety of applications including, for example, structural parts in electric and electronic instruments, industrial machines and transportation machines such as automobiles as well as furnitures and other household commodities.
As is well known, thermoplastic resins have advantages over metallic materials in respect of their good workability, excellent corrosion resistance, lightness in weight and inexpensiveness so that they are useful as a base material for the manufacture of various shaped articles such as structural parts of instruments and machines as well as furnitures and other household commodities.
Thermoplastic resins in general, however are inferior in the mechanical properties such as tensile strength, impact strength and hardness in comparison with metallic materials and are not quite satisfactory in respect of the heat resistance and dimensional stability. Moreover, the usually advantageous feature of lightness in weight may in some cases cause a disadvantage to give a trifling impression as commercial goods.
A proposal has been made to solve the above described problems by compounding a thermoplastic resin with a metallic filler. For example, thermoplastic resins such as polypropylene, polyethylene, polyamide, poly(ethylene terephthalate), poly(butylene terephthalate) and the like are compounded with a fine powder of a metal such as zinc, copper, iron and the like as a filler to give a resin-based composite molding compound.
Shaped articles prepared from such a metal-filled molding compound, however, more or less have an unavoidable serious problem of rusting of the metal particles contained in the shaped article to cause poor appearance or degradation in the mechanical properties when the article is prolongedly kept in humid air, water, soil or other corrosive environment. When rusting occurs in the molding compound before molding, which is usually in the form of pellets, moreover, drawbacks are sometimes caused in the molding work of such a deteriorated molding compound.
Several methods have been proposed to solve this problem including a method of forming a corrosion-resistant coating layer of, for example, a rust inhibitor, metal plating and ceramic on the surface of the shaped article, a method of forming a relatively thick uniform skin layer of a rust-free resin on the surface of the shaped article and a method of wrapping the shaped article with a film of a plastic resin having a small permeability to moisture.
These methods, however, cannot provide a complete solution of the problem. For example, the corrosion-resistant coating layer formed on the surface of a shaped article has a problem of inherently low durability because the coating layer gradually falls off the surface with time. In addition, the productivity of shaped articles must decrease because the process is complicated for forming such a protective surface layer. The method of forming a skin layer is particularly defective when the shaped article has an irregular configuration or non-uniform wall thickness due to the extreme difficulty in obtaining a skin layer of uniform thickness. The productivity of course cannot be high enough. The method of wrapping with a plastic film also suffers low productivity due to the complicated and troublesome process if not to mention the limited applicability of the method.
In addition to the above described problem due to rusting of metal particles, conventional metallic filler-loaded composite molding compounds have problems in the moldability of the compound and stability of the shaped articles therefrom, especially, when the molding compound has a density in excess of 1.5 g/cm3 or, in particular, 2.0 g/cm3. The moldability of such a molding compound is poor so that the appearance of the articles shaped therefrom is sometimes not quite acceptable. Moreover, the shaped articles of such a molding compound usually have relatively low mechanical strengths or, in particular, impact strength and exhibit a large molding shrinkage sometimes with different ratios of shrinkage between directions. Therefore, it is a rather difficult matter to obtain a satisfactory shaped article of high density with good dimensional stability exhibiting no warping distortion from such a metallic filler-loaded molding compound.
Further, degradation of the matrix resin may sometimes take place in such a metallic filler-loaded composite molding compound due to the influence of the metal particles. The molding compound is also not quite satisfactory as a moldable electroconductive material because sufficiently high electroconductivity can hardly be obtained or the reproducibility of the conductivity, if obtained, is usually low.
SUMMARY OF THE INVENTION
An object of the present invention therefore is to provide a novel thermoplastic resin-based molding composition loaded with a metallic filler free from the above described problems and disadvantages in the conventional metallic filler-loaded molding compounds. Namely, the molding composition of the present invention should have good moldability and be capable of giving shaped articles having good appearance and high mechanical properties as well as dimensional stability, electroconductivity and resistance against rusting and also suitable for secondary machining such as cutting, grinding and lathing using standard machine tools.
As a result of the extensive investigations undertaken with the above mentioned object, it has been unexpectedly discovered that the problems can be solved by compounding a thermoplastic resin with a specific amount of a metallic filler after a surface treatment of the particles with a specific amount of a compound belonging to the class of so-called water repellent agents, optionally, with further admixture of a small amount of a low-molecular weight oxidized polypropylene.
Thus, the thermoplastic resin-based molding composition of the present invention comprises:
(A) from 2 to 70 parts by weight of a thermoplastic polymer as the matrix phase; and
(B) from 98 to 30 parts by weight of a metallic filler, of which the particles have a surface coated with a water repellent agent, the amount of the water repellent agent being in the range from 0.01 to 5% or, preferably, from 0.3 to 3% by weight by weight based on the metallic filler before coating therewith.
When the molding composition is additionally admixed with (C) a low-molecular weight oxidized polypropylene, the composition comprises:
(A) from 2 to 70 parts by weight of a thermoplastic polymer;
(B) from 98 to 30 parts by weight of a metallic filler, of which the particles have a surface coated with a water repellent agent, the amount of the water repellent agent being as mentioned above; and
(C) a low-molecular weight oxidized polypropylene in an amount in the range from 0.1 to 2% by weight based on the total amount of the components (A) and (B).
Although the above mentioned metallic filler is usually in a particular form, it is sometimes advantageous that a part of such a particulate filler is replaced with a fibrous filler. Namely, the metallic filler as the component (B) in the above given formulations should be a combination of a particulate metallic filler having an average particle diameter, for example, in the range from 0.1 to 20 μm and a fibrous metallic filler having a fiber diameter in the range from 0.03 to 60 μm or, preferably, from 0.1˜20 μm and an aspect ratio in the range from 50 to 2500 in a weight ratio not exceeding 1:1 or, preferably, in the range from 1:1 to 30:1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The component (A) to form the matrix phase of the inventive molding composition is a thermoplastic polymer which is not limited to a particular type but may be selected from various kinds of thermoplastic resins and elastomers either singly or as a combination of two kinds or more according to need.
The above mentioned thermoplastic resins include polyolefin resins, poly(vinyl chloride) resins, polyamide resins, polyimide resins, polyester resins, polyacetal resins, polycarbonate resins, poly(aromatic ether or thioether) resins, poly(aromatic ester) resins, polysulfone resins, polystyrene resins, acrylic resins, fluorocarbon resins and the like.
The polyolefin resins include homopolymers and copolymers of α-olefins such as ethylene, propylene, butene-1, 1-methyl-butene-1, 3-methylpentene-1, 4-methylpentene-1 and the like as well as copolymers of these monomers as the principal ingredient with another monomer of a different type. Typical examples of the polyolefin resins are high-density, medium-density and low-density polyethylenes, straight-chained polyethylenes, super-high molecular polyethylenes, copolymers of ethylene and vinyl acetate and other ethylene-based polymers, atactic, syndiotactic and isotactic polypropylenes, block and random copolymers of propylene and ethylene and other propylene-based polymers, poly(4-methylpentene-1) and the like.
Further, these polyolefins may be modified by the graft polymerization of a polar vinylic monomer such as α, β-unsaturated carboxylic acids and esters thereof exemplified by acrylic acid, esters of acrylic acid, methacrylic acid, esters of methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid and the like or an unsaturated epoxide exemplified by glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether and the like.
The poly(vinyl chloride) resins include homopolymeric poly(vinyl chloride) resins and copolymeric resins of vinyl chloride with another monomer copolymerizable therewith. The copolymeric resins are exemplified by the copolymers of vinyl chloride and an acrylic acid ester, copolymers of vinyl chloride and a methacrylic acid ester, copolymers of vinyl chloride and ethylene, copolymers of vinyl chloride and propylene, copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride and vinylidene chloride and the like. These poly(vinyl chloride) resins may be post-chlorinated to have an increased content of chlorine.
The polyamide resins include 6-nylon, 12-nylon and the like obtained by the ring-opening polymerization of an aliphatic cyclic lactam, 6,6-nylon, 6,10-nylon, 6,12-nylon and the like obtained by the condensation-polymerization of an aliphatic diamine and an aliphatic dicarboxylic acid, condensation-polymerization of m-xylene and adipic acid and the like obtained by the condensation-polymerization of an aromatic diamine and an aliphatic dicarboxylic acid, condensation-polymerizates of p-phenylene diamine and terephthalic acid or m-phenylene diamine and isophthalic acid and the like obtained by the condensation-polymerization of an aromatic diamine and an aromatic dicarboxylic acid, 11-nylon and the like obtained by the condensation-polymerization of an amino acid, and so on.
The polyimide resins include polyimides and polyamideimides. Exemplary of the polyimides are these obtained from the combinations of pyromellitic anhydride and diamino diphenyl ether, 3,4,3',4'-benzophenone tetracarboxylic acid anhydride and diamino diphenyl ether, bismaleimide and diamino diphenyl methane and the like. Exemplary of the polyamideimides are those obtained from the combination of trimellitic anhydride and diamino diphenyl ether and the like.
The polyester resins include those obtained by the condensation-polymerization of an aromatic dicarboxylic acid and an alkylene glycol exemplified by poly (ethylene terephthalates), poly (methylene terephthalates) and the like.
The polyacetal resins are exemplified by the homopolymeric polyoxymethylenes and copolymers of formaldehyde and ethylene oxide obtained from trioxane and ethylene oxide.
Preferable examples of the polycarbonate resins are the 4,4'-dihydroxy diallyl alkane-based polycarbonates and the bisphenol A-based polycarbonates prepared by the phosgene method, in which bisphenol A and phosgene A and phosgene are reacted, or the ester interchange method, in which bisphenol A and a diester of carbonic acid such as diphenyl carbonate are reacted. Usable polycarbonate resins include those modified or flame-retardant bisphenol A-based polycarbonates obtained by partially replacing the bisphenol A in the above mentioned preparation of unmodified polycarbonates with 2,2-bis (4-hydroxy-3,5-dimethyl phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromo phenyl) propane and the like.
The poly(aromatic ether or thioether) resins have ether linkages or thioether linkages in the polymeric molecular chain and are exemplified by polyphenylene oxides, styrene-grafted polyphenylene oxides, polyphenylene sulfides and the like.
The poly(aromatic ester) resins are exemplified by polyoxybenzoyls obtained by the condensation-polymerization of 4-hydroxy benzoic acid and polyarylates obtained by the condensation-polymerization of bisphenol A and an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid.
The polysulfone resins have sulfone linkages in the polymeric molecular chain and are exemplified by polysulfones obtained by the condensation-polymerization of bisphenol A 4,4'-dichlorodiphenyl sulfone, polyether sulfones having a structure in which phenylene groups are bonded together at the 1,4-positions through ether linkages and sulfone linkages and polyaryl sulfones having a structure in which diphenylene groups and diphenylene ether groups are alternately bonded together through sulfone linkages.
The polystyrene resins include homopolymers of styrene and α-methyl styrene and copolymers thereof as well as copolymers of them as the principal ingredient with another monomer copolymerizable therewith. Typical examples of the polystyrene resins are general-purpose polystyrenes, high-impact polystyrenes, heat-resistant polystyrenes, polymers of α-methyl styrene, copolymers of acrylonitrile, butadiene and styrene (ABS), copolymers of acrylonitrile and styrene (AS), copolymers of acrylonitrile, chlorinated polyethylene and styrene (ACS), copolymers of acrylonitrile, ethylenepropylene rubber and styrene (AES), copolymers of acrylic rubber, acrylonitrile and styrene and the like.
The acrylic resins include polymers of acrylic acid esters and methacrylic acid esters exemplified by methyl, ethyl, n-propyl, isopropyl and butyl esters of acrylic acid and methacrylic acid. Particularly preferable among them are poly(methyl methacrylate) resins from the standpoint of practically using the inventive molding composition as an industrial material.
The fluorocarbon resins include homopolymers of tetrafluoro ethylene, hexafluoro propylene, vinylidene fluoride, vinyl fluoride and the like and copolymers thereof as well as copolymers of these fluorinated monomers as the principal ingredient with another monomer copolymerizable therewith. Exemplary of the fluorocarbon resin are poly(tetrafluoroethylenes), poly(vinylidene fluorides), poly(vinyl fluorides), copolymers of tetrafluoroethylene and ethylene, copolymers of tetrafluoroethylene and vinylidene fluoride, copolymers of hexafluoropropylene and vinylidene fluoride, copolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride and the like.
The elastomeric polymers suitable as the component (A) include natural rubber and various kinds of synthetic rubbers exemplified by polybutadiene rubbers (BR), copolymeric rubbers of styrene and butadiene (SBR), copolymeric rubbers of acrylonitrile and butadiene (NBR), copolymeric rubbers of styrene, butadiene and acrylonitrile, polychloroprene rubbers (CR) and other butadiene-based rubbers, polyisoprene rubbers or synthetic natural rubbers, copolymeric rubbers of isobutylene and isoprene or so-called butyl rubbers (IIR), copolymeric rubbers of acrylonitrile and isoprene, polyisobutylene rubbers, copolymeric rubbers of ethylene and propylene, copolymeric rubbers of ethylene and vinyl acetate, chlorinated polyethylenes, chlorosulfonated polyethylenes, urethane rubbers, silicone rubbers, fluorocarbon rubbers, acrylic rubbers, epichlorohydrin rubbers, propylene oxide rubbers, polyester-based elastomers, polyacrylate-based elastomers, polyolefin-based elastomers, poly-(vinyl chloride)-based elastomers, copolymeric elastomers of styrene and butadiene, polystyrene-based elastomers, polyamide-based elastomers, polyurethane-based elastomers and the like.
The above named polymers can be used either singly or as a mixture of two kinds or more according to need as the component (A) to form the matrix phase of the inventive molding composition. Particularly preferable among them are polyamide resins such as 6-nylon, 6,6-nylon, 12-nylon and the like, polypropylenes and poly(butylene terephthalates).
The components (B) to form the disperse phase in the inventive molding composition is a metallic filler usually in a particulate form. Metals of which the powder as the metallic filler is prepared include zinc, copper, iron, lead, aluminum, nickel, chromium, titanium, manganese, tin, platinum, tungsten, gold, magnesium, cobalt, strontium and the like as well as alloys of these metallic elements such as stainless steel, solder alloys, brass, bronze and the like, of which zinc is particularly preferred. Zinc oxide also can be used. Certain ceramic materials obtained in a powdery form can be used as the filler including silicon carbide, silicon nitride, zirconia, aluminum nitride, titanium carbide and the like.
The metallic filler in a particulate form as the component (B) should have an average particle diameter in the range from 0.2 to 2.0 μm or, preferably, in the range from 0.4 to 10 μm. When the filler particles are too fine, the molding composition compounded with the filler may be poor in the moldability. When the filler particles are too coarse, on the other hand, the molding composition compounded with the filler cannot give a shaped article having a sufficiently high impact strength and free from the drawbacks of warping distortion after molding.
When a particular high impact strength is desired of the shaped article of the inventive molding composition, it is advantageous to replace a part of the above described filler in a particulate form with a fibrous filler. Suitable fibrous fillers include inorganic fibers such as glass fibers, carbon fibers, magnesium sulfate fibers and the like, fibers and whiskers of a metal such as stainless steel, brass, aluminum, nickel and the like, whiskers of ceramics such as potassium titanate, silicon carbide and the like, and organic fibers such as aromatic polyamide fibers, cellulosic fibers, nylon fibers, polyester fibers, polypropylene fibers and the like. Preferable among them are glass fibers, carbon fibers, stainless steel fibers, brass fibers, potassium titanate whiskers, aromatic polyamide fibers and the like. Glass fibers are particularly preferred. These fibrous fibers can be used either singly or as a combination of two kinds or more accordingly to need.
The fibers of the fibrous filler should have a fiber diameter in the range from 0.03 to 60 μm or, preferably, from 0.1˜20 μm and an aspect ratio in the range from 50 to 2500 or, preferably, from 100 to 2000. When the aspect ratio of the fibers is to small, desired improvement in the impact strength of the shaped article cannot be achieved as desired. When the aspect ratio of the fibers is too large, on the other hand, the shaped articles of the molding composition may be subject to an increased molding shrinkage and drawbacks of warping distortion after molding so that the molding composition cannot be used industrially due to the poor dimensional stability of the shaped articles therefrom.
When a particulate filler and a fibrous filler are used in combination as the component (B) in the inventive molding composition, the weight ratio of them should not exceed 1:1 although no substantial improvement can be obtained in the impact strength of the shaped articles molded of the composition when the amount of the fibrous filler is too small. In this regard, the weight ratio of the particulate to fibrous fillers should be in the range from 1:1 to 30:1 or, preferably, from 2:1 to 20:1.
When the inventive molding composition is prepared by compounding the thermoplastic polymer as the component (A) with the filler as the component (B), it is essential that the filler is subjected in advance to a surface treatment with a water repellent agent in a specific amount. Suitable water repellent agents include silane-based coupling agents, titanate-based coupling agents, silicone fluids, higher fatty acids, higher alcohols, waxes and the like, of which silane-based coupling agents, titanate-based coupling agents and silicone fluids are preferred. These water repellent agents can be used either singly or as a combination of two kinds or more according to need.
The type of the above mentioned silane-based coupling agent is not particularly limitative, and any of known ones can be used. Exemplary of suitable silane-based coupling agents are triethoxy silane, vinyl tris (β-methoxyethoxy) silane, 3-methacryloxypropyl trimethoxy silane, 3-glycdyloxypropyl trimethoxy silane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxy silane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxy silane, 3-aminopropyl triethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane, 3-mercaptopropyl trimethoxy silane, 3-chloropropyl trimethoxy silane and the like, of which 3-aminopropyl triethoxy silane and N-(2-aminoethyl)-3-aminopropyl trimethoxy silane are preferred.
The type of the above mentioned titanate-based coupling agents is also not particularly limitative and any of hitherto known ones can be used. Exemplary of suitable titanate-based coupling agents are isopropyl triisostearoyl titanate, isopropyl tri(dodecylbenzene sulfonyl) titanate, isopropyl tris(dioctyl pyrophosphato) titanate, tetraisopropyl bis(dioctylphosphito) titanate, tetraoctyl bis(ditridecyl phosphito) titanate, tetra(2,2-diallyloxy methyl-1-butyl) bis(di-tridecyl phosphito) titanate, bis(dioctyl pyrophosphato) oxyacetate titanate bis(dioctyl pyrophosphato) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri(dioctyl phosphato) titanate, isopropyl, tri(cumyl phenyl) titanate, isopropyl tri(N-amidoethyl aminoethyl) titanate, dicumyl phenyl oxyacetate titanate, di(isostearoyl) ethylene titanate and the like, of which isopropyl triisostearoyl titanate and isopropyl tri(N-amidoethyl amioethyl) titanate are preferred.
Further, suitable silicone fluids include dimethyl silicone fluids, methyl phenyl silicone fluids, polyether-modified silicone fluids, alkyl-modified silicone fluids, methyl hydrogen polysiloxane fluids and the like, of which dimethyl silicone fluids and methyl hydrogen polysiloxane fluids are preferred.
To summarize the description on the types of the water repellent agents, dimethyl silicone fluids, methyl hydrogen polysiloxane fluids and 3-aminopropyl triethoxy silane are particularly preferable as the surface treatment agent of the filler as the component (B) in the inventive molding composition.
The procedure for the surface treatment of the component (B) with the water repellent agent is not particularly limitative according to any known method conventionally undertaken for the surface treatment of a powdery material. A preferable method in respect of the versatility and controllability of the temperature and mixing velocity in the treatment is to use a Henschel mixer in which the water repellent agent is sprayed on to the filler under agitation and thoroughly mixed together.
The water repellent agent in this surface treatment of the filler as the component (B) should be used in an amount in the range from 0.01 to 5% by weight or, preferably, from 0.05 to 3% by weight or, more preferably, from 0.1 to 2% by weight based on the amount of the filler as the component (B) before the surface treatment. When the amount of the water repellent agent is too small, no sufficient coupling effect can be exhibited between the surface of the filler and the matrix phase so that the resultant molding composition would be poor in the moldability. When the amount thereof is too large, on the other hand, a phenomenon of slipping may be caused due to the excessively strong effect of lubrication between the filler surface and the matrix phase leading to disadvantages of decreased productivity of pelletization of the molding composition and decreased workability in the molding works along with a problem of poor appearance of the shaped articles prepared from the composition as a result of strong bleeding of the water repellent agent on the surface of the shaped article.
The fillers thus surface-treated or coated with the water repellent agent as the component (B) can be used either singly or as a combination of two kinds or more according to need. The compounding amount of the component (B) in the inventive molding composition should be in the range from 30 to 98 parts by weight or, preferably, from 50 to 97 parts by weight or, more preferably, from 60 to 95 parts by weight per 100 parts by weight of the total amount of the components (A) and (B).
As is mentioned before, the inventive molding composition can be further admixed with a low-molecular weight oxidized polypropylene as the component (C) in an amount in the range from 0.1 to 2% by weight based on the total amount of the polymeric matrix phase as the component (A) and the filler after the surface treatment as the component (B). The low-molecular weight oxidized polypropylene is prepared by the oxidative degradation of, for example, an isotactic polypropylene as a solid or melt or in the form of a solution with an oxidizing agent such as peroxides. Carboxyl groups and other types of oxygen-containing groups are introduced into the molecular structure of the polypropylene by this oxidizing reaction. By virtue of the carboxyl groups introduced into the molecular structure, the low-molecular weight oxidized polypropylene has increased miscibility with thermoplastic resins having polarity such as polyamides in comparison with non-oxidized low-molecular weight polypropylenes. It is preferable to use a low-molecular weight oxidized polypropylene having an average molecular weight in the range from 1500 to 20000. When admixed with an appropriate amount of such a low-molecular weight oxidized polypropylene, the molding composition is imparted with improved moldability and capable of giving shaped articles having improved mechanical strengths and electric conductivity.
When improvements in the mechanical properties and dimensional stability of shaped articles of the composition are desired, it is sometimes advantageous to admix the composition with a modifier such as a modified polyolefin which serves to increase the affinity between the polymeric matrix as the component (A) and the surface of the filler as the component (B). Suitable polyolefin-based modifiers include, for example, polyethylene and polypropylene modified by graft-polymerization of 0.05 to 20% by weight of a monomer exemplified by unsaturated organic acids and derivatives thereof such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and other organic acids, maleic anhydride, itaconic anhydride, citraconic anhydride and other anhydrides of unsaturated organic acids, methyl acrylate, monomethyl maleate and other esters of unsaturated organic acids, acrylamide, fumaric acid monoamide and other amides of unsaturated organic acids, itaconic acid imide and other imides of unsaturated organic acids, and so on. The modification reaction of the polyolefin by the polymerization of these monomers can be accelerated by an organic peroxide such as benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide and the like.
Usable modifiers in addition to the above described ones include ethylene- or propylene-based polymers modified by graft polymerization of an unsaturated epoxide such as glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, ally glycidyl ether and the like carried out optionally with admixture of a liquid rubber such as a polybutadiene hydroxylated at the molecular chain ends.
The amount of these modifiers added to the inventive molding composition should usually be in the range from 1 to 10% by weight based on the total amount of the components (A) and (B). When the amount thereof is too small, the desired improvement by the addition of the modifier cannot be fully exhibited as a matter of course. When the amount thereof is too large, on the other hand, phase separation may sometimes take place in the shaped article of the composition to greatly decrease the mechanical strengths.
It is optional according to need that the molding composition of the invention is further admixed with various kinds of inorganic and organic fillers though in a limited amount not to substantially affect the desirable properties of the composition or the shaped article prepared therefrom. Such an optional filler may be powdery, granular or fibrous.
Inorganic fillers suitable for the above mentioned optional addition are exemplified by oxides such as silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice, pumice ballons and the like, hydroxides such as aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate and the like, carbonates such as calcium carbonate, magnesium carbonate, dolomite, dawsonite and the like, sulfates and sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite and the like, silicates such as talc, clay, mica, asbestos, glass balloons, glass beads, montmorillonite, bentonite and the like, carbonaceous filler such as carbon black, graphite powder, carbon balloons and the like, molybdenum sulfide, zinc borate, barium metaborate, calcium borate, sodium borate and the like. These inorganic filler can be used either singly or as a combination of two kinds or more according to need.
Organic fillers suitable for the above mentioned optional addition are exemplified by non-fibrous ones such as rice hulls, wood flour, fragments of paper and cellophane and the like. These organic filler also can be used either singly or as a combination of two kinds or more according to need. It is of course optional that inorganic and organic fillers are used in combination.
If desired, the molding composition of the invention can be admixed with various kinds of additives conventionally compounded in resin-based molding compositions including, for example, lubricants, coloring agents, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardant agents, plasticizers, blowing agents and the like according to the intended application of the articles shaped from the molding composition.
The molding composition of the present invention can be prepared by uniformly blending and compounding the components (A) and (B), optionally, together with the component (C) and above described optional additives in a conventional procedure of kneading in a molten condition by using a suitable blending machine such as Henschel mixers, single-or double-screw extruder machines, Banbury mixers, roller mixers and the like, of which Henschel mixers, extruder machines and Bunbury mixers are preferred.
The molding composition of the present invention can be shaped into articles by any conventional molding method such as injection molding, extrusion molding, compression molding and the like without particular limitations by virtue of the good moldability. The composition can give not only shaped articles having complicated configuration as molded but also shaped articles suitable for secondary work-ing to meet various applications by adequately modifying the blending ratio of the components. The application fields of the shaped articles of the inventive molding composition include structural and functional parts in electric and electronic instruments, machines in general, automobiles and the like, furnitures, household commodities and so on. Particularly exemplary of the shaped articles are, for example, all kinds of rotary members for power transmission such as flywheels, gears, pulleys, cams, motors and the like, housing, chassis, turn tables and the like of record players, cassette tape recorders, speaker boxers, etc., sound insulating and shielding materials, vibra-tion dumping materials, shielding materials for electro-magnetic waves, furnitures, kitchenwares, office supplies, toys, fishing implements and so on.
The thermoplastic resin-based molding composition of the present invention is prepared by compounding a thermoplastic polymer as the matrix phase with a metallic filler after a surface treatment with a water repellent agent so that the filler particles dispersed in the polymeric matrix are highly resistant against rusting along with greatly improved affinity between the surface of the filler particles and the matrix polymer. Accordingly, the inventive molding composition has good moldability and is capable of giving shaped articles having outstandingly good outer appearance, excellent mechanical properties, high dimensional stability without warping distortion and stable electric conductivity. By virtue of the improved moldability, the inventive molding composition can be shaped into articles having large dimensions or a complicated configuration and the shaped articles have good secondary workability suitable for machining with standard machine tools such as cutting, grinding, lathing and the like. Thus, present invention provides a material having excellent moldability into shaped articles and machinability of the shaped articles in combination. Such a combination of moldability and machinability is the very great advantage of the inventive molding composition never obtained in any of conventional resin-based molding composition and metals.
In the following, examples are given to illustrate the inventive molding compositions in more detail but not to limit the scope of the invention in any way.
In the examples given below, the polymeric materials used as the polymeric matrix of the molding compositions include the commercially available products listed below, each of which is referred to hereinbelow with the abridged symbols of the name preceding the name of the polymeric material.
(1) 6-PA: 6-nylon, LM-102, a product by Kanegafuchi Chemical Industry Co.
(2) 66-PA: 6,6-nylon, 1200S, a product by Asahi Chemical Industry Co.
(3) 12-PA: 12-nylon, 3014U, a product by Ube Kosan Co.
(4) MXDA: Polyamide, 6002, a product by Mitsubishi Gas Chemical Co.
(5) PP: polypropylene, J2000G, a product by Idemitsu Petro-chemical Co.
(6) PBT: poly(butylene terephthalate), 5010, a product by Mitsubishi Chemical Industries Co.
(7) PET: poly(ethylene terephthalate), MA 2101, a product by Unitika Co.
(8) POM: polyacetal, 3010, a product by Asahi Chemical Industry Co.
(9) polystyrene, HT-53, a product by Idemitsu Petro-chemical CO.
(10) PE: polyethylene, 110J, a product by Idemitsu Petro-chemical Co. having a melt index of 14 g/10 minutes
(11) ABS: copolymeric resin of acrylonitrile, butadiene and styrene, JSR-35, a product by Japan Synthetic Rubber Co.
(12) PC: polycarbonate, N-2500, a product by Idemitsu Petro-chemical Co.
(13) PVC: poly(vinyl chloride), JZ-102F, a product by Shin-Etsu Polymer Co.
(14) PMMA: poly(methyl methacrylate), 50N, a product by Asahi Chemical Industry Co.
(15) PPO: poly(phenylene oxide), 731J, product by Engineering Plastics Co.
(16) PSO: polysulfone, P-1700, a product by Nissan Chemical Co.
(17) PI: polyimide, SP-1, a product by DuPont Far East Co.
(18) SBR: styrene-butadiene rubber, JSR-1500, a product by Japan Synthetic Rubber Co.
(19) EPR: ethylene-propylene copolymeric rubber, EP-07P, a product by Japan Synthetic Rubber Co.
(20) SR: silicone rubber, KE-931U, a product by Shin-Etsu Chemical Co.
(21) EVA: ethylene-vinyl acetate copolymer rubber, Evatate D-3021, a product by Sumitomo Chemical Co.
(22) PEE: polyester-based elastomer, Belprene P-40B, a product by Toyo Spinning Co.
(23) POE: polyolefin-based elastomer, TPE-1500, a product by Sumitomo Chemical Co.
Further, in the following examples, various kinds of fillers were used as listed below.
(1) ZN: zinc powder having an average particle diameter of about 3 μm, a product by Sakai Chemical Co.
(2) ZnO: zinc oxide having an average particle diameter of about 3 μm, a product by Sakai Chemical CO.
(3) CU: copper powder having an average particle diameter of about 5 μm, a product by Fukuda Kinzoku Hakufun Kogyo Co.
(4) α-FE: iron powder having an average particle diameter of about 0.5 μm, a product by Dowa Teppun Kogyo Co.
(5) α-Fe2 O3 : iron oxide powder having an average particle diameter of about 0.5 μm, a product by Dowa Teppun Kogyo Co.
(6) Ni: nickel powder having an average particle diameter of about 3 μm
(7) Pb: lead powder having an average particle diameter of 10 μm
(8) Al: aluminum powder having an average particle diameter of about 10 μm
(9) Sn: tin powder having an average particle diameter of about 7 μm
(10) SnO2 : tin oxide powder having an average particle diameter of about 3 μm
(11) SS: stainless steel powder having an average particle diameter of about 10 μm
(12) SA: powder of solder alloy having an average particle diameter of about 8 μm
(13) BR: brass powder having an average particle diameter of about 10 μm
(14) SF: stainless steel fibers having a diameter of 10 μm and fiber length of 6 mm
(15) NF: nickel fibers having a diameter of 10 μm and fiber length of 8 mm
(16) PT: whiskers of potassium titanate having a diameter of 0.3 μm and length of 15 μm
(17) ZrO2 : zirconia powder having an average particle diameter of about 0.5 μm
The above listed fillers were used each after a surface treatment with one of the water repellent agents shown below.
A: 3-aminopropyl triethoxy silane, a product by Nippon Unicar Co.
B: N-(2-aminoethyl)-3-aminopropyl trimethoxy silane, a product by Nippon Unicar Co.
C: methyl hydrogen polysiloxane fluid, a product by Shin-Etsu Chemical Co.
D: dimethyl silicone fluid, a product by Shin-Etsu Chemical Co.
E: isopropyl triisostearoyl titanate, a product by Ajinomoto Co.
F: isopropyl tri (N-amidoethyl aminoethyl) titanate, a product by Ajinomoto Co.
G: finely divided silica powder having an average particle diameter of about 12 μm, a product by Nippon Aerosil Co.
H: finely divided silica powder having an average particle diameter of about 7 μm, a product by Nippon Aerosil Co.
I: stearic acid
J: stearyl alcohol
K: polyethylene wax
EXAMPLE 1
A 0.3 part by weight of 3-aminopropyl triethoxy silane was sprayed to 100 parts by weight of a zinc powder having an average particle diameter of 3 μm contained in a Henschel mixer of 20 liter capacity and the mixer was run for 5 minutes at a velocity of 1000 rpm to mix them together at a temperature of 60° to 100° C. to prepare a surface-coated zinc powder. Thereafter, a 6-PA resin in an amount of 50 % by weight based on the surface-coated zinc powder was added to the mixer and melted and mixed together by running the mixer for 15 minutes at a velocity of 2000 rpm and at a temperature of 200° to 300° C. to give a composite molding resin composition with further admixture of 0.3% by weight of an antioxidant (Irganox 1010, a product by Ciba Geigy Co.), 0.3% by weight of calcium stearate as a lubricant (a product by Nippon Yushi Co.) and 1.0% by weight of carbon black (DL-600, a product by Lion Akzo Co.), each amount being based on the total amount of the 6-PA resin and the surface-coated zinc powder.
The thus obtained molding composition was pelletized by using a single-screw extruder machine (Model NVC-50, manufactured by Nakatani Machinery Co.) operated at a temperature of 200° to 300° C. with a rate of extrusion of 30 kg/hour and the pellets were shaped into test plates by injection molding using an injection molding machine (Model FS-160S; manufactured by Nissei Resin Industry Co.) at a temperature of 200° to 300° C.
The test plates were subjected to the evaluation of various properties including the following items each according to the procedure described below. The results are shown in Table 1.
(1) Resistance against rusting
A test plate of 75 mm by 75 mm wide and 3.2 mm thick was put into a bag made of a polyethylene film of 40 μm thickness and, after sealing of the opening by welding, the bag was heated for 100 hours or 300 hours in an atmosphere of 95% relative humidity at 60° C. The test plate taken out of the bag was inspected for the surface condition with naked eyes or by using a magnifying lens of 25 magnification to give the results in four ratings of A, B, C and D according to the following criteria.
A: no rust found under magnifying lens
B: powder-like rust found under magnifying lens
C: small number of rust speckles found with naked eyes
D: large number of rust speckles found with naked eyes
(2) Moldability
A box having outer dimensions of 150 mm by 80 mm by 80 mm with a wall thickness of 5 mm was shaped from the molding composition by injection molding using the same injection molding machine as used in the preparation of the test plates above to determine the critical impregnation pressure or minimum impregnation pressure for short shot in kg/cm2. The thus molded boxes were visually inspected for the outer appearance and the results were expressed in three ratings of A, B and C according to the following criteria.
A: beautiful and acceptable
B: small number of silver marks found
C: large number of silver marks found
(3) Izod impact strength
Measurement was performed according to ASTM D-1302 to give the results in kg cm/cm.
(4) Electric resistance
Measurement was performed according to JIS C 1302 by using an automatic insulation-resistance tester (Model F-535F, manufactured by Fuso Electric Co.) with a voltage impression of 500 volts DC to give the total resistance in megaohm.
EXAMPLES 2 TO 65 AND COMPARATIVE EXAMPLES 1 TO 6
The experimental procedure in each of these Examples and Comparative Examples was substantially the same as in Example 1 using the same zinc powder as the filler expecting replacement of the 6-PA resin as the matrix polymer and the 3-aminopropyl triethoxy silane as the water repellent agent each with the material shown in Table 1 in an amount also indicated in the same table. In the formulations shown in Table 1, the amounts of the filler and the matrix polymer given in parts by weight are given per 100 parts by weight of the total amount of the filler after the surface treatment and the matrix polymer and the amount of the water repellent agent given in % by weight is based on the amount of the filler before the surface treatment. The molding compositions prepared in Comparative Examples 2 and 4 were disadvantageous in respect of the low productivity in pelletization due to slipping. Table 1 also shows the results of the evaluation of the products carried out in the same manner as in Example 1. In Examples 64 and 65, the zinc powder as the filler and the finely divided silica powder as the water repellent agent were dry-blended in the Henschel mixer operated at a velocity of 1000 rpm for 5 minutes at a temperature of 60° to 100° C. before the addition of the 6-PA resin.
                                  TABLE 1                                 
__________________________________________________________________________
                               Moldability        Elec-                   
           Water               Mini-              tric                    
           repellent                                                      
                Matrix         mum    Izod impact test                    
                                                  resis-                  
Filler     agent                                                          
                polymer                                                   
                       Rust after                                         
                               pres-                                      
                                   Ap-      Un-   ance,                   
(parts by  (% by                                                          
                (parts by                                                 
                       100 300 sure,                                      
                                   pear-                                  
                                      Notched,                            
                                            notched,                      
                                                  mega-                   
weight)    weight)                                                        
                weight)                                                   
                       hours                                              
                           hours                                          
                               kg/cm.sup.2                                
                                   ance                                   
                                      kg · cm/cm                 
                                            kg · cm/cm           
                                                  ohm                     
__________________________________________________________________________
Exam-                                                                     
    1 Zn (50)                                                             
           A (0.3)                                                        
                6-PA (50)                                                 
                       A   A   31  A  10.2  62    16                      
ple 2 Zn (70)                                                             
           A (0.3)                                                        
                6-PA (30)                                                 
                       A   A   34  A  8.9   53    14                      
    3 Zn (90)                                                             
           A (0.3)                                                        
                6-PA (10)                                                 
                       A   A   40  A  7.5   46    0.5                     
    4 Zn (95)                                                             
           A (0.3)                                                        
                6-PA (5)                                                  
                       A   A   45  B  5.7   33    0.3                     
    5 Zn (90)                                                             
           A (1.0)                                                        
                6-PA (10)                                                 
                       A   A   39  A  7.6   46    0.4                     
    6 Zn (90)                                                             
           A (3.0)                                                        
                6-PA (10)                                                 
                       A   A   35  A  7.9   48    0.3                     
    7 Zn (90)                                                             
           A (0.3)                                                        
                66-PA (10)                                                
                       A   A   42  A  7.4   48    0.7                     
    8 Zn (70)                                                             
           A (0.3)                                                        
                PP (30)                                                   
                       A   A   34  A  10.0  78    13                      
    9 Zn (80)                                                             
           A (0.3)                                                        
                PP (20)                                                   
                       A   A   37  A  8.1   70    10                      
    10                                                                    
      Zn (95)                                                             
           A (0.3)                                                        
                PP (5) A   A   42  A  7.4   61    0.5                     
    11                                                                    
      Zn (90)                                                             
           A (0.3)                                                        
                PBT (10)                                                  
                       A   A   45  A  6.7   41    0.6                     
    12                                                                    
      Zn (90)                                                             
           A (0.3)                                                        
                PET (10)                                                  
                       A   A   46  A  6.1   42    1.1                     
    13                                                                    
      Zn (90)                                                             
           A (0.3)                                                        
                POM (10)                                                  
                       A   A   43  A  7.7   47    0.9                     
    14                                                                    
      Zn (90)                                                             
           A (0.3)                                                        
                PE (10)                                                   
                       A   A   39  A  9.2   77    2.7                     
    15                                                                    
      Zn (90)                                                             
           A (0.3)                                                        
                ABS (10)                                                  
                       A   A   41  A  11.4  73    1.6                     
Exam-                                                                     
    18                                                                    
      Zn (90)                                                             
           B (0.3)                                                        
                6-PA (10)                                                 
                       A   A   41  A  6.9   41    0.5                     
ple 19                                                                    
      Zn (90)                                                             
           C (0.05)                                                       
                6-PA (10)                                                 
                       A   B   49  A  6.7   43    12                      
    20                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                6-PA (10)                                                 
                       A   A   41  A  7.1   44    0.3                     
    21                                                                    
      Zn (90)                                                             
           C (2.0)                                                        
                6-PA (10)                                                 
                       A   A   39  A  7.7   47    0.4                     
    22                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                PP (10)                                                   
                       A   A   37  A  8.7   52    0.9                     
    23                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                PBT (10)                                                  
                       A   A   39  A  6.9   40    0.7                     
    24                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                POM (10)                                                  
                       A   A   37  A  6.9   49    0.7                     
    25                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                ABS (10)                                                  
                       A   A   37  A  11.7  71    0.6                     
    44                                                                    
      Zn (90)                                                             
           D (0.5)                                                        
                6-PA (10)                                                 
                       A   A   43  A  6.4   40    1.2                     
    62                                                                    
      Zn (90)                                                             
           E (0.5)                                                        
                6-PA (10)                                                 
                       A   A   44  A  6.1   37    1.7                     
    63                                                                    
      Zn (90)                                                             
           F (0.5)                                                        
                6-PA (10)                                                 
                       A   A   44  A  6.0   37    2.0                     
    17                                                                    
      Zn (90)                                                             
           A (0.5)                                                        
                6-PA/PP =                                                 
                       A   A   43  A  7.9   48    1.2                     
                5/5 (10)                                                  
    27                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                6-PA/PET =                                                
                       A   A   45  A  6.3   41    1.5                     
                5/5 (10)                                                  
    28                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                12-PA (10)                                                
                       A   A   35  A  6.6   41    0.3                     
    29                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                PS (10)                                                   
                       A   A   42  A  6.1   40    0.3                     
Exam-                                                                     
    30                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                PC (10)                                                   
                       A   A   44  A  11.9  77    1.5                     
ple 31                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                PVC (10)                                                  
                       A   A   37  A  9.7   70    0.2                     
    32                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                PMMA (10)                                                 
                       A   A   33  A  5.9   37    2.4                     
    33                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                PPO (10)                                                  
                       A   A   44  A  6.3   44    1.1                     
    34                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                PSO (10)                                                  
                       A   A   51  A  7.1   45    1.0                     
    35                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                PI (10)                                                   
                       A   A   51  A  7.4   60    1.7                     
    36                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                PPS (10)                                                  
                       A   A   53  A  6.2   43    1.9                     
    37                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                SBR (10)                                                  
                       A   A   37  A  17.1  105   0.1                     
    38                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                EPR (10)                                                  
                       A   A   32  A  14.9  90    0.1                     
    39                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                SR (10)                                                   
                       A   A   40  A  13.7  88    3.3                     
    40                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                EVA (10)                                                  
                       A   A   35  A  15.2  94    0.4                     
    41                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                PEE (10)                                                  
                       A   A   39  A  11.7  75    0.5                     
    42                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                POE (10)                                                  
                       A   A   36  A  14.2  89    0.5                     
    64                                                                    
      Zn (90)                                                             
           G (0.5)                                                        
                6-PA (10)                                                 
                       A   A   39  A  6.3   42    0.9                     
    65                                                                    
      Zn (90)                                                             
           H (0.5)                                                        
                6-PA (10)                                                 
                       A   A   38  A  6.5   44    0.8                     
Exam-                                                                     
    45                                                                    
      Zn (50)                                                             
           D (0.5)                                                        
                66-PA (50)                                                
                       A   A   34  A  11.5  64    15                      
ple 46                                                                    
      Zn (70)                                                             
           D (0.5)                                                        
                66-PA (30)                                                
                       A   A   35  A  9.2   56    14                      
    47                                                                    
      Zn (90)                                                             
           D (0.5)                                                        
                66-PA (10)                                                
                       A   A   41  A  7.5   49    0.7                     
    48                                                                    
      Zn (95)                                                             
           D (0.5)                                                        
                66-PA (5)                                                 
                       A   A   47  A  5.9   35    0.3                     
    49                                                                    
      Zn (90)                                                             
           D (1.0)                                                        
                66-PA (10)                                                
                       A   A   39  A  7.9   50    0.7                     
    50                                                                    
      Zn (90)                                                             
           D (3.0)                                                        
                66-PA (10)                                                
                       A   A   37  A  8.0   51    0.6                     
    51                                                                    
      Zn (50)                                                             
           D (0.5)                                                        
                12-PA (50)                                                
                       A   A   30  A  9.7   55    14                      
    52                                                                    
      Zn (90)                                                             
           D (0.5)                                                        
                12-PA (30)                                                
                       A   A   32  A  8.0   49    12                      
    53                                                                    
      Zn (90)                                                             
           D (0.5)                                                        
                12-PA (10)                                                
                       A   A   33  A  6.9   44    0.3                     
    54                                                                    
      Zn (95)                                                             
           D (0.5)                                                        
                12-PA (5)                                                 
                       A   A   39  A  5.0   30    0.3                     
    55                                                                    
      Zn (90)                                                             
           D (1.0)                                                        
                12-PA (10)                                                
                       A   A   31  A  7.0   45    0.3                     
    56                                                                    
      Zn (90)                                                             
           D (3.0)                                                        
                12-PA (10)                                                
                       A   A   30  A  7.1   45    0.3                     
    16                                                                    
      Zn (90)                                                             
           D (3.0)                                                        
                12-PA (10)                                                
                       A   A   34  A  6.7   42    0.4                     
    26                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                66-PA (10)                                                
                       A   A   41  A  7.5   50    0.7                     
    57                                                                    
      Zn (90)                                                             
           D (0.5)                                                        
                66-PA (10)                                                
                       A   A   35  A  8.9   54    0.6                     
Exam-                                                                     
    58                                                                    
      Zn (90)                                                             
           D (0.5)                                                        
                66-PA (10)                                                
                       A   A   37  A  7.0   41    0.6                     
ple 43                                                                    
      Zn (90)                                                             
           C (0.5)                                                        
                6PA/PP =                                                  
                       A   A   42  A  8.1   50    1.1                     
                5/5 (10)                                                  
    59                                                                    
      Zn (90)                                                             
           D (0.5)                                                        
                6-PA/PP =                                                 
                       A   A   40  A  8.2   53    1.0                     
                5/5 (10)                                                  
    60                                                                    
      Zn (70)                                                             
           D (0.5)                                                        
                6-PA/PP =                                                 
                       A   A   33  A  8.9   54    15                      
                5/5 (30)                                                  
    61                                                                    
      Zn (50)                                                             
           D (0.5)                                                        
                6-PA/PP =                                                 
                       A   A   30  A  10.5  64    16                      
                5/5 (50)                                                  
Com-                                                                      
    1 Zn (90)                                                             
           A (0.005)                                                      
                6-PA (10)                                                 
                       C   D   51  C  4.3   19    1.0                     
par-                                                                      
    2 Zn (90)                                                             
           A (6.0)                                                        
                6-PA (10)                                                 
                       A   A   35  C  6.1   41    29                      
ative                                                                     
    3 Zn (90)                                                             
           C (0.005)                                                      
                6-PA (10)                                                 
                       C   D   67  B  4.7   22    35                      
Exam-                                                                     
    4 Zn (90)                                                             
           C (6.0)                                                        
                6-PA (10)                                                 
                       A   A   35  C  6.0   39    27                      
ple 5 Zn (25)                                                             
           A (0.3)                                                        
                6-PA (75)                                                 
                       A   A   28  A  13.1  73    100<.sup.--             
    6 Zn (99)                                                             
           A (0.3)                                                        
                6-PA (1)                                                  
                       B   C   61  C  1.9   10    40                      
__________________________________________________________________________
EXAMPLES 66 TO 103 AND COMPARATIVE EXAMPLES 7 TO 13
The experimental procedure in each of these Examples and Comparative Examples was substantially the same as in Example 1. Table 2 below shows the formulation of the molding compositions and the results of evaluation undertaken in the same manner as in Example 1. Examples 104 to 107 and Comparative Examples 14 and 15.
A molding resin composition was prepared by first blending, in a Henschel mixer of 20 liter capacity, 15 parts by weight of a 6-PA resin, 85 parts by weight of a ZnO powder having a varied average particle diameter shown in Table 3 below, 0.5 part by weight of a low-molecular oxidized polypropylene having an average molecular weight of 3500 and 0.3 part by weight of an aminosilane-based coupling agent and then kneading the blend thoroughly at 220° to 350° C. in a double-screw kneading machine (Model NAS-50, manufactured by Nakatani Machinery Co.).
The thus prepared molding resin composition were each shaped by injection molding into test plates at 220° to 350° C. using the same injection molding machine as used in Example 1. The molding compositions were evaluated by measuring the minimum molding pressure in the injection molding of the composition and the mechanical and electrical properties of the test plates in the following manner. The results are shown in Table 3.
                                  TABLE 2                                 
__________________________________________________________________________
                                    Moldability            Elec-          
                Water               Mini-                  tric           
                repellent                                                 
                     Matrix         mum     Izod impact                   
                                                           resist-        
        Filler  agent                                                     
                     polymer                                              
                           Rust after                                     
                                    pres-                                 
                                        Ap-        Un-     ance,          
        (parts by                                                         
                (% by                                                     
                     (parts by                                            
                           100  300 sure,                                 
                                        pear-                             
                                            Notched,                      
                                                   notched,               
                                                           mega-          
        weight) weight)                                                   
                     weight)                                              
                           hours                                          
                                hours                                     
                                    kg/cm.sup.2                           
                                        ance                              
                                            kg · cm/cm           
                                                   kg · cm/cm    
                                                           ohm            
__________________________________________________________________________
Exam-                                                                     
     66 ZnO (90)                                                          
                C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   43  A   7.1    42      --             
ple  71 ZnO (90)                                                          
                A (0.5)                                                   
                     6-PA (10)                                            
                           A    A   41  A   7.0    42      --             
     84 Cu (90) C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   47  A   8.7    48      17             
     85 Cu (90) A (0.5)                                                   
                     6-PA (10)                                            
                           A    A   45  A   8.9    50      19             
     86 Fe (90) C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   48  A   6.1    39      15             
     87 Fe (90) A (0.5)                                                   
                     6-PA (10)                                            
                           A    A   44  A   6.3    40      15             
     88 Fe.sub.2 O.sub.3 (90)                                             
                C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   49  A   5.7    38      5.4            
     89 Fe.sub.2 O.sub.3 (90)                                             
                A (0.5)                                                   
                     6-PA (10)                                            
                           A    A   44  A   5.9    41      7.0            
     90 Zn/Fe.sub.2 O.sub.3 =                                             
                A (0.5)                                                   
                     6-PA (10)                                            
                           A    A   44  A   6.0    35      0.7            
        45/45 (90)                                                        
     91 Zn/ZnO =                                                          
                C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   40  A   7.2    44      1.0            
        70/20 (90)                                                        
     92 Ni (90) C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   43  A   6.4    35      0.2            
     93 Pb (90) C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   42  A   7.9    48      1.4            
     94 Al (90) C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   39  A   8.2    50      1.9            
     95 Sn (90) C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   44  A   7.1    44      0.3            
Exam-                                                                     
     96 SnO.sub.2 (90)                                                    
                C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   46  A   6.0    38      0.3            
ple  97 SnO.sub.2 (90)                                                    
                C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   39  A   6.4    44      0.2            
     98 SnO.sub.2 (90)                                                    
                C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   37  A   7.2    46      0.5            
     99 SnO.sub.2 (90)                                                    
                C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   38  A   6.6    45      0.3            
     100                                                                  
        SnO.sub.2 (90)                                                    
                C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   52  A   5.4    35      0.1            
     101                                                                  
        SnO.sub.2 (90)                                                    
                C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   51  A   5.9    37      0.1            
     102                                                                  
        SnO.sub.2 (90)                                                    
                C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   42  A   6.7    41      0.9            
     103                                                                  
        SnO.sub.2 (90)                                                    
                C (0.5)                                                   
                     6-PA (10)                                            
                           A    A   47  A   6.9    45      2.1            
Compa-                                                                    
     7  Fe.sub.2 O.sub.3 (90)                                             
                C (0.005)                                                 
                     6-PA (10)                                            
                           C    D   69  C   1.7    12      50             
rative                                                                    
     8  Fe.sub.2 O.sub.3 (90)                                             
                A (0.005)                                                 
                     6-PA (10)                                            
                           C    D   71  C   2.3    14      70             
Exam-                                                                     
     9  Zn (90) A (0.5)                                                   
                     6-PA (10)                                            
                           B    C   59  B   4.3    21      75             
ple  10 Zn (90) C (0.5)                                                   
                     6-PA (10)                                            
                           A    B   62  B   3.1    16      10             
     11 Zn (90) G (0.5)                                                   
                     6-PA (10)                                            
                           C    D   57  B   3.2    17      100<           
     12 Fe.sub.2 O.sub.3 (90)                                             
                A (0.5)                                                   
                     6-PA (10)                                            
                           B    C   61  B   2.0    15      100<           
     13 Fe (90) C (0.5)                                                   
                     6-PA (10)                                            
                           B    B   64  B   2.3    16      11             
__________________________________________________________________________
(1) Molding pressure: a box having dimensions of 90 mm by 150 mm by 70 mm with a wall thickness of 5 mm and a pin gate of 1 mm diameter was shaped by injection molding under the above mentioned conditions to determine the minimum pressure for impregnation in kg/cm2 G.
(2) Mechanical properties: tensile strength in kg/cm2 of the test plates was determined according to ASTM D-638 and flexural strength and elastic modules by bending each in kg/cm2 were determined according to ASTM D-790.
(3) Electrical properties: specific resistance in ohm-cm was determined according to Japan Rubber Association Standard SRJS-2301-1969.
                                  TABLE 3                                 
__________________________________________________________________________
        Average               Elastic                                     
        Particle                                                          
               Molding                                                    
                    Tensile                                               
                         Flexural                                         
                              modulus by                                  
                                     Specific                             
        diameter                                                          
               pressure,                                                  
                    strength,                                             
                         strength,                                        
                              bending, ×                            
                                     resistance,                          
        of ZnO, μm                                                     
               kg/cm.sup.2 G                                              
                    kg/cm.sup.2                                           
                         kg/cm.sup.2                                      
                              10.sup.4 kg/cm.sup.2                        
                                     ohm · cm                    
__________________________________________________________________________
Example                                                                   
     104                                                                  
        0.3    75   860  1510 12.8   1 × 10.sup.5                   
     105                                                                  
        1      70   810  1450 12.5   1 × 10.sup.5                   
     106                                                                  
        3      67   795  1320 11.7   1 × 10.sup.5                   
     107                                                                  
        5      65   710  1250 10.9   1 × 10.sup.5                   
Compar-                                                                   
     14 0.1    97   905  1570 13.1    1 × 10.sup.5 *                
ative                                                                     
     15 9      60   650   990 9.1    1 × 10.sup.5                   
Example                                                                   
__________________________________________________________________________
 *large variation in the values of specific resistance
In these Examples and Comparative Examples, the low-molecular oxidized polypropylene was a commercial product (Biscol TS-200, a product by Sanyo Kasei Co.) and the aminosilane-based coupling agent was aminopropyl triethoxy silane. Examples 108 to 110 and Comparative Example 16 and 17.
The formulation and experimental procedure in each of these Examples and Comparative Examples were substantially the same as in Examples 104 to 107 except that the amounts of the 6-PA resin and ZnO, having an average particle diameter of 2 μm, were varied as shown in Table 4 below, which also shows the results of evaluation of the molding resin compositions carried out in the same manner as in the preceding examples.
                                  TABLE 4                                 
__________________________________________________________________________
        6-PA,                                                             
            ZnO,               Elastic                                    
        parts                                                             
            parts                                                         
                Molding                                                   
                     Tensile                                              
                          Flexural                                        
                               modulus by                                 
                                      Specific                            
        by  by  pressure,                                                 
                     strength,                                            
                          strength,                                       
                               bending, ×                           
                                      resistance,                         
        weight                                                            
            weight                                                        
                kg/cm.sup.2 G                                             
                     kg/cm.sup.2                                          
                          kg/cm.sup.2                                     
                               10.sup.4 kg/cm.sup.2                       
                                      ohm · cm                   
__________________________________________________________________________
Example                                                                   
     108                                                                  
        40  60  61   870  1550 9.2    1 × 10.sup.7                  
     109                                                                  
        20  80  68   875  1470 12.1   1 × 10.sup.5                  
     110                                                                  
         5  95  74   760  1350 13.5   1 × 10.sup.4                  
Compar-                                                                   
      16                                                                  
        60  40  49   920  1660 7.4     1 × 10.sup.11                
ative                                                                     
      17                                                                  
         3  97  150  620  1290 14.6   1 × 10.sup.4                  
Example                                                                   
__________________________________________________________________________
EXAMPLES111 TO 113 AND COMPARATIVE EXAMPLES18 AND 19
The formulation and experimental procedure were substantially the same as in the preceding examples except that the amounts of the 6-PA resin and ZnO filler were 15 parts by weight and 85 parts by weight, respectively, in each of these Examples and Comparative Examples and the amount of the low-molecular oxidized polypropylene, referred to as the component (C) hereinbelow, was varied as indicated in Table 5 below, which also shows the results of evaluation of the molding resin compositions carried out in the same manner as in the preceding examples.
                                  TABLE 5                                 
__________________________________________________________________________
        Component            Elastic                                      
        (C),  Molding                                                     
                   Tensile                                                
                        Flexural                                          
                             modulus by                                   
                                    Specific                              
        parts by                                                          
              pressure,                                                   
                   strength,                                              
                        strength,                                         
                             bending, ×                             
                                    resistance,                           
        weight                                                            
              kg/cm.sup.2 G                                               
                   kg/cm.sup.2                                            
                        kg/cm.sup.2                                       
                             10.sup.4 kg/cm.sup.2                         
                                    ohm · cm                     
__________________________________________________________________________
Example                                                                   
     111                                                                  
        0.1   90   705  1120 10.1   1 × 10.sup.5                    
     112                                                                  
        0.7   67   830  1490 12.7   1 × 10.sup.5                    
     113                                                                  
        1.5   59   755  1300 11.6   1 × 10.sup.5                    
Compar-                                                                   
      18                                                                  
        0.05  120  520   950 9.7    1 × 10.sup.7                    
ative                                                                     
      19                                                                  
        2.5   51   670   970 9.6    1 × 10.sup.5                    
Example                                                                   
__________________________________________________________________________
EXAMPLES 114 TO 117
The formulation and experimental procedure in each of these Examples were substantially the same as in the preceding examples except that the amount of the component (C) was always 0.5 part by weight and, instead, the average molecular weight thereof was varied as indicated in Table 6 given below, which also shows the results of evaluation of the molding resin compositions carried out in the same manner as in the preceding examples.
                                  TABLE 6                                 
__________________________________________________________________________
        Average                                                           
        molecular            Elastic                                      
        weight of                                                         
              Molding                                                     
                   Tensile                                                
                        Flexural                                          
                             modulus by                                   
                                    Specific                              
        component                                                         
              pressure,                                                   
                   strength,                                              
                        strength,                                         
                             bending, ×                             
                                    resistance,                           
        (C)   g/cm.sup.2 G                                                
                   kg/cm.sup.2                                            
                        kg/cm.sup.2                                       
                             10.sup.4 kg/cm.sup.2                         
                                    ohm · cm                     
__________________________________________________________________________
Example                                                                   
     114                                                                  
        7000  75   815  1460 12.7   1 × 10.sup.5                    
     115                                                                  
        15000 72   820  1470 12.9   1 × 10.sup.5                    
     116                                                                  
        20000 80   830  1500 13.1   1 × 10.sup.5                    
     117                                                                  
        25000 90   845  1510 13.4   1 × 10.sup.5                    
__________________________________________________________________________
EXAMPLES 118 TO 120 AND COMPARATIVE EXAMPLES 20 AND 21
The formulation and experimental procedure in each of these Examples and Comparative Examples were substantially the same as in the preceding examples except that the low-molecular oxidized polypropylene as the component (C) always has an average molecular weight of 3500 and amount of the 3-aminopropyl triethoxy silane as the aminosilane-based coupling agent was varied as indicated in Table 7 below, which also shows the results of evaluation of the molding resin compositions carried out in the same manner as in the preceding examples.
                                  TABLE 7                                 
__________________________________________________________________________
       Aminosi-             Elastic                                       
       lane,                                                              
            Molding                                                       
                  Tensile                                                 
                       Flexural                                           
                            modulus by                                    
                                  Specific                                
       parts by                                                           
            pressure,                                                     
                  strength,                                               
                       strength,                                          
                            bending, ×                              
                                  resistance,                             
       weight                                                             
            kg/cm.sup.2 G                                                 
                  kg/cm.sup.2                                             
                       kg/cm.sup.2                                        
                            10.sup.4 kg/cm.sup.2                          
                                  ohm · cm                       
__________________________________________________________________________
Example                                                                   
118    0.1  87    760  1310 11.9  1 × 10.sup.5                      
119    0.7  65    830  1490 13.0  1 × 10.sup.5                      
120    1.5  61    760  1310 12.1  1 × 10.sup.5                      
Comparative                                                               
Example                                                                   
20     0.05 105   550  970  10.1  1 × 10.sup.7                      
21     2.5  57    720  960  10.5  1 × 10.sup.8 *                    
__________________________________________________________________________
 *large variation in the values as measured   EXAMPLES 121 TO 134
The formulation and experimental procedure in each of these Examples were substantially the same as in the preceding Examples except that the amount of the 3-aminopropyl triethoxy silane was always 0.3 part by weight and the thermoplastic resin, taken in an amount of 15 parts by weight, was not the 6-PA resin but one of the polymers or a combination of two polymers in a proportion as indicated in Table 8 below, which also shows the results of evaluation of the molding compositions carried out in the same manner as in the preceding examples. The values of specific resistance of the test plates were each 1×105 ohm·cm.
                                  TABLE 8                                 
__________________________________________________________________________
                               Elastic                                    
               Molding                                                    
                     Tensile                                              
                          Flexural                                        
                               modulus by                                 
Polymer(s)     pressure,                                                  
                     strength,                                            
                          strength,                                       
                               bending, ×                           
(ratio by weight)                                                         
               kg/cm.sup.2 G                                              
                     kg/cm.sup.2                                          
                          kg/cm.sup.2                                     
                               10.sup.4 kg/cm.sup.2                       
__________________________________________________________________________
Example                                                                   
121   66-PA    73    820  1470 12.9                                       
122   MXDA     75    840  1500 13.0                                       
123   PET      73    890  1620 13.4                                       
124   PBT      74    795  1240 11.1                                       
125   PPO      77    810  1450 12.7                                       
126   PC       76    835  1490 12.9                                       
127   ABS      67    720  1150 10.1                                       
128   POM      70    805  1390 12.0                                       
129   PP       47    510  910  6.2                                        
130   PE       44    460  810  5.4                                        
131   PPO/6-PA (9:6)                                                      
               74    830  1490 12.9                                       
132   PC/PET (10:5)                                                       
               74    870  1520 12.9                                       
133   PBT/PET (9:6)                                                       
               74    850  1430 12.7                                       
134   PSO      85    810  1350 13.1                                       
__________________________________________________________________________
EXAMPLES 135 TO 139
The formulation and experimental procedure in each of these Examples were substantially the same as in the preceding Examples except that the polymer for the matrix was one of those indicated in Table 9 below and 0.3 part by weight of 3-aminopropyl triethoxy silane was replaced with 0.5 part by weight of a dimethyl silicone fluid. Table 9 below also shows the results of evaluation of the molding resin compositions carried out in the same manner as in the preceding examples. The values of specific resistance of the test plates were each 1×105 ohm·cm.
              TABLE 9                                                     
______________________________________                                    
                                     Elastic                              
           Molding   Tensile  Flexural                                    
                                     modulus by                           
Poly-      pressure, strength,                                            
                              strength,                                   
                                     bending, ×                     
mer        kg/cm.sup.2 G                                                  
                     kg/cm.sup.2                                          
                              kg/cm.sup.2                                 
                                     10.sup.4 kg/cm.sup.2                 
______________________________________                                    
Example                                                                   
135    6-PA    65        795    1390   12.3                               
136    12-PA   61        720    1190   11.7                               
137    66-PA   71        835    1510   13.1                               
138    PBT     71        815    1290   11.9                               
139    PP      44        525    990    6.4                                
______________________________________
EXAMPLES 140 TO 144
The formulation and experimental procedure in each of these Examples were substantially the same as in the preceding Examples except that the polymer for the matrix phase was one of those indicated in Table 10 below and the dimethyl silicone fluid was replaced with the same amount of isopropyl triisostearoyl titanate as a titanate-based coupling agent. Table 10 below also shows the results of evaluation of the molding resin compositions carried out in the same manner as in the preceding examples. The values of specific resistance of the test plates were each 1×105 ohm·cm.
              TABLE 10                                                    
______________________________________                                    
                                     Elastic                              
           Molding   Tensile  Flexural                                    
                                     modulus by                           
Poly-      pressure, strength,                                            
                              strength,                                   
                                     bending, ×                     
mer        kg/cm.sup.2 G                                                  
                     kg/cm.sup.2                                          
                              kg/cm.sup.2                                 
                                     10.sup.4 kg/cm.sup.2                 
______________________________________                                    
Example                                                                   
140    6-PA    71        805    1410   12.9                               
141    12-PA   66        700    1190   10.1                               
142    66-PA   72        840    1530   13.3                               
143    PBT     73        815    1280   12.0                               
144    PP      46        510    975    6.1                                
______________________________________
PREPARATION EXAMPLE 1 (PREPARATION OF MODIFIED POLYPROPYLENE)
Into a three-necked flask equipped with a stirrer, thermometer and reflux condenser and having a separable cover were introduced 100 parts by weight of a polypropylene resin having a density of 0.91 g/cm3 and a melt index MI of 8 g/10 minutes (J700G, a product by Idemitsu Petrochemical Co.), 5 parts by weight of a 1,4-polybutadiene having a number-average molecular weight of 3000 and terminated at each molecular chain end with a hydroxy group (Poly bd R45HT, a product by ARCO Chem. Div.), 20 parts by weight of maleic anhydride, 1.72 parts by weight of dicumyl peroxide and 600 parts by weight of xylene and the mixture was heated under agitation at 120° C. for 1 hour and then at 140° C. for 3 hours to effect the reaction.
After completion of the reaction, the reaction mixture was poured into a large volume of acetone and the precipitates formed in acetone were collected by filtration with suction and dried at 70° C. for 50 hours to give a white powder. This powder was subjected to extraction with acetone in a Soxhlet extractor for 16 hours to give a modified polypropylene as the product by removing unreacted polybutadiene and maleic anhydride.
EXAMPLES 145 TO 172 AND COMPARATIVE EXAMPLES 22 TO 29
A Henschel mixer was charged with 10 parts by weight of one of the fibrous fillers indicated in Table 11, 70 parts by weight of a zinc powder having an average particle diameter of about 3 μm and 0.5 part by weight of a dimethyl silicone fluid and operated at a velocity of 1000 rpm for 5 minutes at a temperature of 60° to 100° C. to coat the surface of the fibers and zinc particles with the silicone fluid. Thereafter, 20 parts by weight of a 6-PA resin were introduced into the mixer and thoroughly blended together. The thus obtained blend was further kneaded at 220° to 350° C. in a double-screw extruder machine to give a molding resin composition which was then shaped into test plates at 220° to 350° C. by injection molding using the same injection machine as used in Example 1. The molding resin composition were evaluated for the moldability of the composition, mechanical properties of the test plates, molding shrinkage of the molded articles and warping distortion of the molded articles in the following manner.
(1) Moldability of the molding composition
A box having dimension of 90 mm by 70 mm with a wall thickness of 5 mm and a pin gate of 1 mm diameter was shaped from the molding composition by injection molding using an injection molding machine (Model IS-125, manufactured by Toshiba Machines Co.) operated under the standard conditions of a cylinder temperature of 200° to 300° C., temperature of metal mold of 75° to 100° C., injection pressure of 60 kg/cm2 and shot time of 20 seconds and the moldability of the molding composition was evaluated according to the following criteria in three ratings in terms of the reproducibility of the box configuration by the injection molding and the injection pressure.
A: quite satisfactory
B: appearance of sink marks at some portions, somewhat higher injection pressure than the standard pressure
C: partly incomplete box configuration, injection pressure of 100 kg/cm2 G or higher
(2) Mechanical properties of the test plates
Tensile strength was determined according to ASTM D-638, Izod impact value was determined according to ASTM D-256 and flexural strength and elastic modules by bending were determined according to ASTM D-790.
(3) Molding shrinkage of molded articles
Square test plates of 76 mm by 76 mm wide and 3.2 mm thick were shaped from the molding composition by injection molding under a sufficiently high injection pressure and the changes of the dimensions in % were determined in the molding direction (MD) and transverse direction (TD).
(4) Warping distortion of shaped articles
A circular disc of 45 mm diameter and 2 mm thickness was shaped by injection molding under the same conditions as above and warping of the disc was evaluated by the height α of the highest point when the disc was placed on a horizontal plane. The results were given in three ratings of A, B, C according to the following criteria.
A: α<0.5 mm
B: 0.5 mm ≦α≦1 mm
C: α>1 mm
Table 11 given below shows the formulation of the molding resin compositions and the results of the evaluation thereof performed in the above described manner. In Table 11, the kinds of the fibrous fillers are indicated with the symbols of GF, SF, BF, PT, CF, SCF and APAF for glass fibers, stainless steel fibers, brass fibers, whiskers of potassium titanate, carbon fibers, silicone carbide fibers and aromatic polyamide fibers, respectively.
                                  TABLE 11                                
__________________________________________________________________________
                               Izod                                       
       Fibrous filler     Tensile                                         
                               impact                                     
                                     Flexural                             
           Length,                                                        
                Diameter,                                                 
                      Aspect                                              
                          strength,                                       
                               value,                                     
                                     strength,                            
       Kind                                                               
           mm   μm ratio                                               
                          kg/cm.sup.2                                     
                               kg · cm/cm                        
                                     kg/cm.sup.2                          
__________________________________________________________________________
Example                                                                   
145    GF  10   4     2500                                                
                          1650 101   2450                                 
146        10   13    770 1550 94    2300                                 
147        6    4     1500                                                
                          1600 97    2350                                 
148        6    13    462 1570 94    2250                                 
149        3    4     750 1530 94    2280                                 
150        3    12    231 1500 94    2200                                 
151        1    4     250 1500 90    2150                                 
152        1    13    77  1350 80    2050                                 
153    SF  10   30    333 1450 77    1900                                 
154        10   60    167 1300 73    1810                                 
155        6    30    200 1330 73    1800                                 
156        6    60    100 1200 66    1760                                 
157        3    30    100 1200 65    1720                                 
158        3    60    50  1150 60    1670                                 
159    BF  10   30    333 1430 75    1900                                 
160        10   60    167 1290 71    1820                                 
161        6    30    200 1300 71    1790                                 
162        6    60    100 1210 66    1720                                 
163        3    30    100 1190 64    1710                                 
164        3    60    50  1110 61    1650                                 
__________________________________________________________________________
       Elastic                                                            
       modulus by                                                         
       bending, ×                                                   
             Molding shrinkage, %                                         
                          Warping    Density,                             
       10.sup.4 kg/cm.sup.2                                               
             MD     TD    distortion                                      
                               Moldability                                
                                     g/cm.sup.3                           
__________________________________________________________________________
Example                                                                   
145    12.7  0.82   0.45  B    B     3.21                                 
146    12.2  0.80   0.45  A    A     3.21                                 
147    12.0  0.79   0.45  A    A     3.21                                 
148    12.1  0.80   0.45  A    A     3.21                                 
149    12.1  0.80   0.45  A    A     3.21                                 
150    11.5  0.82   0.52  A    A     3.21                                 
151    10.9  0.82   0.51  A    A     3.21                                 
152    10.1  0.85   0.60  A    A     3.21                                 
153    12.5  0.91   0.55  A    A     3.49                                 
154    12.0  0.89   0.54  A    A     3.49                                 
155    11.9  0.86   0.54  A    A     3.49                                 
156    11.6  0.85   0.58  A    A     3.49                                 
157    11.6  0.85   0.57  A    A     3.49                                 
158    11.3  0.85   0.61  A    A     3.49                                 
159    12.7  0.92   0.57  A    A     3.50                                 
160    11.9  0.90   0.55  A    A     3.50                                 
161    11.9  0.87   0.54  A    A     3.50                                 
162    11.4  0.86   0.56  A    A     3.50                                 
163    11.4  0.85   0.58  A    A     3.50                                 
164    11.1  0.85   0.63  A    A     3.50                                 
__________________________________________________________________________
                               Izod                                       
       Fibrous filler     Tensile                                         
                               impact                                     
                                     Flexural                             
           Length,                                                        
                Diameter,                                                 
                      Aspect                                              
                          strength,                                       
                               value,                                     
                                     strength,                            
       Kind                                                               
           mm   μm ratio                                               
                          kg/cm.sup.2                                     
                               kg · cm/cm                        
                                     kg/cm.sup.2                          
__________________________________________________________________________
Example                                                                   
165    PT  0.01 0.1   100 1250 100   1750                                 
166        0.02 0.1   200 1310 105   1810                                 
167    CF  10   10    1000                                                
                          1820 109   1950                                 
168        3    10    300 1650 102   1800                                 
169    SCF 10   10    1000                                                
                          2030 111   2590                                 
170        3    10    300 1910 104   2400                                 
171    APAF                                                               
           6    12    500 1850 109   2100                                 
172        3    12    250 1710 104   1980                                 
Comparative                                                               
Example                                                                   
22     GF  12   4     3000                                                
                          1710 105   2550                                 
23         0.12 4     30  820  51    1270                                 
24     SF  30   10    3000                                                
                          1500 79    2050                                 
25         0.3  10    30  710  47    980                                  
26     BF  30   10    3000                                                
                          1410 71    1990                                 
27         0.3  10    30  660  40    900                                  
28     CF  30   10    3000                                                
                          1900 110   2050                                 
29         0.3  10    30  790  59    1110                                 
__________________________________________________________________________
       Elastic                                                            
       modulus by                                                         
       bending, ×                                                   
             Molding shrinkage, %                                         
                          Warping    Density,                             
       10.sup.4 kg/cm.sup.2                                               
             MD     TD    distortion                                      
                               Moldability                                
                                     g/cm.sup.3                           
__________________________________________________________________________
Example                                                                   
165    10.0  0.75   0.44  A    A     3.30                                 
166    10.5  0.75   0.45  A    A     3.30                                 
167    9.7   0.80   0.45  A    A     2.97                                 
168    8.1   0.80   0.45  A    A     2.97                                 
169    15.4  0.78   0.42  A    A     3.28                                 
170    14.2  0.80   0.44  A    A     3.28                                 
171    10.9  0.80   0.45  A    A     2.92                                 
172    9.2   0.80   0.45  A    A     2.92                                 
Comparative                                                               
Example                                                                   
22     12.9  0.90   0.45  C    B     3.21                                 
23     7.7   0.79   0.57  A    A     3.21                                 
24     12.7  0.93   0.55  C    B     3.49                                 
25     7.1   0.81   0.59  A    A     3.49                                 
26     12.4  0.93   0.55  C    B     3.50                                 
27     6.9   0.82   0.59  A    A     3.50                                 
28     10.6  0.89   0.43  C    B     2.97                                 
29     8.2   0.75   0.42  A    A     2.97                                 
__________________________________________________________________________
EXAMPLES 173 TO 183 AND COMPARATIVE EXAMPLES 30 TO 39
The experimental procedure in each of these Examples and Comparative Examples was substantially the same as in the preceding examples except that each of the molding resin composition was compounded from 20 parts by weight of the 6-PA resin, a varied amount as indicated in Table 12 below of a zinc powder having an average particle diameter of about 3 μm and a varied amount of a fibrous filler, i.e. glass fibers (GF), stainless steel fibers (SF), potassium titanate whiskers (PT) or carbon fibers (CF), as indicated in Table 12. The results of the evaluation of these molding resin composition are also shown in Table 12 for the same items as in Table 11 in the preceding examples.
                                  TABLE 12                                
__________________________________________________________________________
       Zinc                  Izod                                         
       powder,                                                            
            Fibrous filler                                                
                        Tensile                                           
                             impact                                       
                                   Flexural                               
       parts by                                                           
               Aspect                                                     
                   Parts by                                               
                        strength,                                         
                             value,                                       
                                   strength,                              
       weight                                                             
            Kind                                                          
               ratio                                                      
                   weight                                                 
                        kg/cm.sup.2                                       
                             kg · cm/cm                          
                                   kg/cm.sup.2                            
__________________________________________________________________________
Example                                                                   
173    75   GF 750 5    1270 80    1770                                   
174    50      750 30   1890 110   2670                                   
175    75      231 5    1210 80    1690                                   
176    50      231 30   1820 97    2570                                   
177    75   SF 200 5    1110 69    1520                                   
178    50      200 30   1690 87    2050                                   
179    75   PT 200 5    1190 90    1620                                   
180    50      200 30   1590 118   2300                                   
181    75   CF 300 5    1400 91    1690                                   
182    50      300 30   1870 105   2010                                   
183    30      300 40   1990 111   2220                                   
Comparative                                                               
Example                                                                   
30     79   GF 750 1    870  59    1260                                   
31     20      750 60   2110 115   2790                                   
32     79      231 1    800  57    1200                                   
33     20   SF 231 60   2050 111   2550                                   
34     79      200 1    810  47    1020                                   
35     20      200 60   1820 89    2560                                   
36     79   PT 200 1    770  79    1090                                   
37     20      200 60   1780 121   2520                                   
38     79   CF 300 1    900  79    1110                                   
39     20      300 60   2110 114   2300                                   
__________________________________________________________________________
       Elastic                                                            
       modulus by                                                         
       bending, ×                                                   
             Molding shrinkage, %                                         
                         Warping    Density,                              
       10.sup.4 kg/cm.sup.2                                               
             MD    TD    distortion                                       
                              Moldability                                 
                                    g/cm.sup.3                            
__________________________________________________________________________
Example                                                                   
173    10.9  0.85  0.50  A    A     3.34                                  
174    13.2  0.75  0.44  A    A     2.80                                  
175    10.1  0.85  0.51  A    A     3.34                                  
176    12.7  0.74  0.43  A    A     2.80                                  
177    10.0  0.88  0.55  A    A     3.45                                  
178    12.1  0.79  0.50  A    A     3.52                                  
179    8.9   0.79  0.47  A    A     3.39                                  
180    12.2  0.71  0.41  A    A     3.02                                  
181    7.2   0.83  0.46  A    A     3.20                                  
182    10.9  0.77  0.44  A    A     2.30                                  
183    11.7  0.76  0.44  A    A     1.75                                  
Comparative                                                               
Example                                                                   
30     8.2   1.00  0.81  C    A     3.45                                  
31     15.4  0.70  0.41  A    C     2.48                                  
32     7.9   1.01  0.83  C    A     3.45                                  
33     14.0  0.73  0.42  A    C     2.48                                  
34     7.9   1.00  0.82  C    A     3.47                                  
35     13.7  0.75  0.47  A    C     3.56                                  
36     7.1   1.00  0.79  C    A     3.45                                  
37     13.9  0.70  0.40  A    C     2.77                                  
38     6.2   1.01  0.80  C    A     3.41                                  
39     12.8  0.75  0.43  A    C     1.89                                  
__________________________________________________________________________
EXAMPLES 184 TO 204 AND COMPARATIVE EXAMPLES 40 TO 45
The experimental procedure in each of these Examples and Comparative Examples was substantially the same as in the preceding examples except that the molding resin composition were each compounded from 20 parts by weight of the 6-PA resin, 10 parts by weight of glass fibers having an aspect ratio of 231 and 70 parts by weight of a particulate filler indicated in Table 13 below, which also shows the results of the evaluation of the molding compositions.
EXAMPLES 205 to 223.
The experimental procedure in each of these Examples was substantially the same as in Examples 145 to 172 except that the molding resin composition were each compounded from 10 parts by weight of glass fibers having an aspect ratio of 231, 70 parts by weight of zinc powder having an average particle diameter of about 3 μm and 20 parts by weight of one kind or a combination of two kinds of the thermoplastic resins indicated in Table 14 below, which also shows the results of the evaluation of the molding composition. When two kinds of the thermoplastic resins were used, they were taken in equal amounts.
                                  TABLE 13                                
__________________________________________________________________________
       Particulate filler                                                 
              Average                                                     
                   Izod                                                   
              particle                                                    
                   impact                                                 
              diameter,                                                   
                   strength,                                              
                         Warping    Density,                              
       Kind   μm                                                       
                   kg · cm/cm                                    
                         distortion                                       
                              Moldability                                 
                                    g/cm.sup.3                            
__________________________________________________________________________
Example                                                                   
184    Zinc   0.5  105   A    A     3.21                                  
185           10   82    A    A     3.21                                  
186    Zinc oxide                                                         
              0.5  113   A    A     2.86                                  
187           3    97    A    A     2.86                                  
188           10   76    A    A     2.86                                  
189    Iron   0.7  101   A    A     3.32                                  
190           3    89    A    A     3.32                                  
191           10   80    A    A     3.32                                  
192    Ferrite                                                            
              0.5  100   A    A     2.86                                  
193           3    89    A    A     2.86                                  
194           10   81    A    A     2.86                                  
195    Stainless                                                          
              0.5  96    A    A     3.32                                  
196    steel  3    84    A    A     3.32                                  
197           10   77    A    A     3.32                                  
198    Brass  0.5  97    A    A     3.39                                  
199           3    84    A    A     3.39                                  
200           10   78    A    A     3.39                                  
201    Lead   5    89    A    A     3.65                                  
202    Solder alloy                                                       
              5    92    A    A     3.37                                  
203    Copper 5    86    A    A     3.45                                  
204    Nickel 5    86    A    A     3.44                                  
Comparative                                                               
Example                                                                   
40     Zinc oxide                                                         
              0.1  113   A    C     2.94                                  
41            25   60    C    A     2.94                                  
42     Iron   0.1  109   A    C     3.32                                  
43            30   61    C    A     3.32                                  
44     Ferrite                                                            
              0.1  105   A    C     2.86                                  
45            30   62    C    A     2.86                                  
__________________________________________________________________________

                                  TABLE 14                                
__________________________________________________________________________
                          Elasti                                          
               Izod       modulus                                         
                                Molding                                   
                                      Warp-                               
Exam-     Tensile                                                         
               impact                                                     
                     Flexural                                             
                          by bend-                                        
                                shrinkage,                                
                                      ing     Den-                        
ple       strength,                                                       
               strength,                                                  
                     Strength,                                            
                          ing, × 10.sup.4                           
                                %     distor-                             
                                          Molda-                          
                                              sity,                       
No. Resins                                                                
          kg/cm.sup.2                                                     
               kg · cm/cm                                        
                     kg/cm.sup.2                                          
                          kg/cm.sup.2                                     
                                MD TD tion                                
                                          bility                          
                                              g/cm.sup.3                  
__________________________________________________________________________
205 66-PA 1590 80    2300 12.1  0.80                                      
                                   0.50                                   
                                      A   A   3.21                        
206 MXDA  1580 93    2250 12.9  0.71                                      
                                   0.42                                   
                                      A   A   3.21                        
207 PBT   1200 85    1750 11.1  0.70                                      
                                   0.41                                   
                                      A   A   3.47                        
208 PET   1620 90    1800 11.2  0.70                                      
                                   0.42                                   
                                      A   A   3.33                        
209 PC    1490 155   1910 10.9  0.75                                      
                                   0.45                                   
                                      A   A   3.31                        
210 POM   1410 95    1900 11.9  0.82                                      
                                   0.51                                   
                                      A   A   3.60                        
211 ABS   1020 110   1500 9.9   0.72                                      
                                   0.44                                   
                                      A   A   3.07                        
212 PP    690  65    850  5.7   0.89                                      
                                   0.62                                   
                                      A   A   2.80                        
213 PE    620  50    790  4.9   0.91                                      
                                   0.67                                   
                                      A   A   2.91                        
214 PVC   650  31    970  10.1  0.85                                      
                                   0.50                                   
                                      A   A   3.52                        
215 PMMA  710  30    1520 12.9  0.86                                      
                                   0.52                                   
                                      A   A   3.30                        
216 PI    1280 95    2310 13.9  0.69                                      
                                   0.39                                   
                                      A   A   3.63                        
217 PSO   1370 92    2010 12.1  0.85                                      
                                   0.55                                   
                                      A   A   3.37                        
218 PPO   1490 115   1870 10.2  0.77                                      
                                   0.46                                   
                                      A   A   3.08                        
219 6-PA/PET                                                              
          1600 88    2050 11.2  0.77                                      
                                   0.48                                   
                                      A   A   3.28                        
220 6-PA/PPO                                                              
          1510 97    2000 11.0  0.80                                      
                                   0.49                                   
                                      A   A   3.15                        
221 6-PA/PBT                                                              
          1350 87    1970 11.2  0.75                                      
                                   0.45                                   
                                      A   A   3.20                        
222 PC/PET                                                                
          1590 111   1860 11.1  0.73                                      
                                   0.43                                   
                                      A   A   3.34                        
223 PPS   1510 87    2700 21.7  0.51                                      
                                   0.33                                   
                                      A   A   3.83                        
__________________________________________________________________________
EXAMPLES 224 TO 243
The experimental procedure in each of these Examples was substantially the same as in Examples 145 to 172 except that the molding composition were each compounded from 10 parts by weight of glass fibers having an aspect ratio of 231 as a fibrous filler, a varied amount indicated in Table 15 below of a powder of zinc (Examples 224 to 233) or zinc oxide (Examples 234 to 243) each having an average particle diameter of about 3 μm as a particulate filler and a varied amount of a thermoplastic resin indicated in Table 15, which also shows the results of the evaluation of the molding compositions.
                                  TABLE 15                                
__________________________________________________________________________
Particu-                                                                  
late     Resin       Izod  Flex-                                          
                                Elastic                                   
                                      Molding                             
                                            Warp-                         
Exam-                                                                     
    filler, Parts                                                         
                Tensile                                                   
                     impact                                               
                           ural modulus by                                
                                      shrinkage,                          
                                            ing     Den-                  
ple parts by                                                              
            by  strength,                                                 
                     strength,                                            
                           strength,                                      
                                bending ×                           
                                      %     distor-                       
                                                Molda-                    
                                                    sity,                 
No. weight                                                                
         Kind                                                             
            weight                                                        
                kg/cm.sup.2                                               
                     kg · cm/cm                                  
                           kg/cm.sup.2                                    
                                10.sup.4 kg/cm.sup.2                      
                                      MD TD tion                          
                                                bility                    
                                                    g/cm.sup.3            
__________________________________________________________________________
224 85   6-PA                                                             
            5   1110 77    1750 13.9  0.70                                
                                         0.41                             
                                            A   A   4.99                  
225 60   6-PA                                                             
            30  1650 95    2350 10.3  0.85                                
                                         0.53                             
                                            A   A   3.80                  
226 85   PBT                                                              
            5   850  67    1250 13.1  0.66                                
                                         0.37                             
                                            A   A   5.13                  
227 60   PBT                                                              
            30  1350 95    1900 9.1   0.75                                
                                         0.45                             
                                            A   A   2.85                  
228 85   PET                                                              
            5   1210 69    1360 13.2  0.67                                
                                         0.37                             
                                            A   A   5.05                  
229 60   PET                                                              
            30  1790 99    1950 9.2   0.76                                
                                         0.45                             
                                            A   A   2.71                  
230 85   PPO                                                              
            5   1100 90    1370 12.2  0.72                                
                                         0.44                             
                                            A   A   4.90                  
231 60   PPO                                                              
            30  1640 118   2030 8.2   0.81                                
                                         0.52                             
                                            A   A   3.53                  
232 85   PC 5   1090 110   1410 12.9  0.67                                
                                         0.38                             
                                            A   A   5.05                  
233 60   PC 30  1650 165   2060 8.9   0.79                                
                                         0.48                             
                                            A   A   2.71                  
234 85   6-PA                                                             
            5   1330 97    1930 15.4  0.69                                
                                         0.40                             
                                            A   A   4.04                  
235 60   6-PA                                                             
            30  1830 115   2550 11.7  0.83                                
                                         0.52                             
                                            A   A   2.40                  
236 85   PBT                                                              
            5   1050 87    1440 14.6  0.66                                
                                         0.36                             
                                            A   A   4.13                  
237 60   PBT                                                              
            30  1550 115   2090 10.5  0.74                                
                                         0.45                             
                                            A   A   2.60                  
238 85   PET                                                              
            5   1400 89    1510 14.6  0.66                                
                                         0.57                             
                                            A   A   4.08                  
239 60   PET                                                              
            30  1950 119   2140 10.6  0.75                                
                                         0.43                             
                                            A   A   2.50                  
240 85   PPO                                                              
            5   1290 110   1570 13.6  0.70                                
                                         0.42                             
                                            A   A   3.99                  
241 60   PPO                                                              
            30  1870 138   2220 9.7   0.80                                
                                         0.51                             
                                            A   A   2.28                  
242 85   PC 5   1290 130   1630 13.4  0.65                                
                                         0.37                             
                                            A   A   4.08                  
243 60   PC 30  1830 190   2230 10.3  0.77                                
                                         0.46                             
                                            A   A   4.08                  
__________________________________________________________________________
EXAMPLES 244 TO 251
The experimental procedure in each of these Examples was substantially the same as in Examples 145 to 172 except that the molding resin compositions were each compounded from 10 parts by weight of glass fibers having an aspect ratio of 231 ,70 parts by weight of a zinc powder having an average particle diameter of about 3 μm and 20 parts by weight of a thermoplastic resin indicated in Table 16 below without or with further admixture of 2 parts by weight of the modified polypropylene resin prepared in Preparation Example 1 as a modifier. The fibrous and particulate fillers were used after a surface treatment with 0.5 part by weight of a dimethyl silicone fluid as the water repellent agent. Table 16 below also shows the results of the evaluation of the molding compositions.
                                  TABLE 16                                
__________________________________________________________________________
              Izod impact                                                 
Example       strength,                                                   
                    Warping    Density,                                   
No.  Resin                                                                
         Modifier                                                         
              kg · cm/cm                                         
                    distortion                                            
                         Moldability                                      
                               g/cm.sup.3                                 
__________________________________________________________________________
244  6-PA                                                                 
         Yes  106   A    A     3.20                                       
245  PBT Yes  98    A    A     3.46                                       
246  PET Yes  103   A    A     3.31                                       
247  PPO Yes  122   A    A     3.06                                       
248  PC  Yes  175   A    A     3.30                                       
249  66-PA                                                                
         No   97    A    A     3.20                                       
250  12-PA                                                                
         No   87    A    A     3.00                                       
251  PP  No   69    A    A     2.80                                       
__________________________________________________________________________
EXAMPLES 252 TO 261
The experimental procedure in each of these Examples was substantially the same as in Examples 244 to 251 using the thermoplastic resin indicated in Table 17 below excepting replacement of the zinc powder with the same amount of a zinc oxide powder having an average particle diameter of about 3 μm. Table 17 also shows the results of the evaluation of the molding compositions.
                                  TABLE 17                                
__________________________________________________________________________
              Izod impact                                                 
Example       strength,                                                   
                    Warping    Density,                                   
No.  Resin                                                                
         Modifier                                                         
              kg · cm/cm                                         
                    distortion                                            
                         Moldability                                      
                               g/cm.sup.3                                 
__________________________________________________________________________
252  6-PA                                                                 
         Yes  117   A    A     2.86                                       
253  PET Yes  122   A    A     2.94                                       
254  PPO Yes  137   A    A     2.75                                       
255  PC  Yes  200<  A    A     2.74                                       
256  PET No   117   A    A     2.94                                       
257  PPO No   130   A    A     2.75                                       
258  PC  No   200<  A    A     2.74                                       
259  66-PA                                                                
         No   119   A    A     2.86                                       
260  12-PA                                                                
         No   98    A    A     2.76                                       
261  PP  No   81    A    A     2.58                                       
__________________________________________________________________________

Claims (25)

What is claimed is:
1. A thermoplastic polymeric molding composition which comprises:
(A) from 2 to 70 parts by weight of a thermoplastic polymer as the matrix phase;
(B) from 98 to 30 parts by weight of a metallic filler, of which the particles have a surface coated with a water repellent agent, the amount of the water repellent agent being in the range from 0.01 to 5% by weight based on the metallic filler before coating therewith;
(C) a polypropylene-based polymer which is selected from the group consisting of a low-molecular weight polypropylene containing carboxyl groups which have been introduced into the polypropylene by oxidation thereof, added in an amount in the range of from 0.1 to 2% by weight based on the total amount of the components (A) and (b); and a polypropylene modified by a monomer selected from the group consisting of unsaturated organic acids, anhydrides thereof, esters thereof and amides thereof, added in an amount in the range of 1 to 10% by weight based on the total amount of components (A) and (B); and
wherein the metallic filler as the component (B) is a powder of zinc oxide.
2. A thermoplastic polymeric molding composition which comprises:
(A) from 2 to 70 parts by weight of a thermoplastic polymer as the matrix:
(B) from 98 to 30 parts by weight of a filler which is a combination of
(B-1) a metallic particulate filler having an average particle diameter in the range from 0.1 to 20 μm,
(B-2) a fibrous filler having an aspect ratio in the range from 50 to 2500, in a weight ratio of (B-1): (B-2) in the range from 1:1 to 30:1, the surface of the particles of the component (B-1) and the fibers of the component (B-2) being coated with a water repellent agent in an amount in the range of from 0.01 to 5% by weight based on the total amount of the components (B-1) and (B-2) before coating therewith, and
(C) a polypropylene-based polymer which is selected from the group consisting of a low-molecular weight polypropylene containing carboxyl groups which have been introduced into the polypropylene by oxidation thereof, added in an amount in the range from 0.1 to 2% by weight based on the total amount of the components (A) and (B); and a polypropylene modified by a monomer selected from the group consisting of unsaturated organic acids, anhydrides thereof, esters thereof and amides thereof, added in an amount in the range from 1 to 10 % by weight based on the total amount of the components (A) and (B); and
wherein the metallic particulate filler as the component (B-1) is a powder of zinc oxide.
3. A thermoplastic polymeric molding composition which comprises:
(A) from 2 to 70 parts by weight of a thermoplastic polymer as the matrix phase;
(B) from 98 to 30 parts by weight of a metallic filler, of which the particles have a surface coated with a water repellent agent, the amount of the water repellent agent being in the range from 0.01 to 5% by weight based on the metallic filler before coating therewith;
(C) a polypropylene-based polymer which is selected from the group consisting of a low-molecular weight polypropylene containing carboxyl groups which have been introduced into the polypropylene by oxidation thereof, added in an amount in the range of from 0.1 to 2% by weight based on the total amount of the components (A) and (b); and a polypropylene modified by a monomer selected from the group consisting of unsaturated organic acids, anhydrides thereof, esters thereof and amides thereof, added in an amount in the range of 1 to 10% by weight based on the total amount of components (A) and (B); and
wherein the thermoplastic resin is a polyamide resin selected from the group consisting of 6-nylon, 6,6-nylon, 12-nylon, 6,10-nylon, and 6,12-nylon.
4. A thermoplastic polymeric molding composition which comprises:
(A) from 2 to 70 parts by weight of a thermoplastic polymer as the matrix phase;
(B) from 98 to 30 parts by weight of a metallic filler, of which the particles have a surface coated with a water repellent agent, the amount of the water repellent agent being in the range from 0.01 to 5% by weight based on the metallic filler before coating therewith;
(C) a polypropylene-based polymer which is selected from the group consisting of a low-molecular weight polypropylene containing carboxyl groups which have been introduced into the polypropylene of oxidation thereof, added in an amount in the range of from 0.1 to 2% by weight based on the total amount of the components (A) and (b); and a polypropylene modified by a monomer selected from the group consisting of unsaturated organic acids, anhydrides thereof, esters thereof and amides thereof, added in an amount in the range of 1 to 10% by weight based on the total amount of components (A) and (B); and
wherein the thermoplastic resin is a polypropylene.
5. The thermoplastic polymeric molding composition as claimed in claim 1 wherein the low-molecular weight oxidized polypropylene as the component (C) has an average molecular weight in the range from 1500 to 2000.
6. The thermoplastic polymer molding composition as claimed in claim 5 which comprises as component (C) the low-molecular oxidized polypropylene in an amount in the range from 0.1 to 2% by weight based on the total amount of the components (A) and (B).
7. The thermoplastic polymeric molding composition as claimed in claim 1 wherein the thermoplastic polymer is selected from the group consisting of polyamide resins, polypropylenes and poly(butylene terephthalates).
8. The thermoplastic polymeric molding composition as claimed in claim 1 wherein the water repellent agent is selected from the group consisting of silane coupling agents, titanate coupling agents and silicone fluids.
9. The thermoplastic polymeric molding composition as claimed in claim 1 wherein the water repellent agent is selected from the group consisting of 3-aminopropyl triethoxy silane, N-(2-aminoethyl)-3-aminopropyl trimethoxy silane, isopropyl triisostearoyl titanate, isopropyl tri(N-aminoethyl aminoethyl) titanate, dimethyl silicone fluids and methyl hydrogen polysiloxanes.
10. The thermoplastic polymeric molding composition as claimed in claim 2 wherein the low-molecular weight oxidized polypropylene as the component (C) has an average molecular weight in the range from 1500 to 20000.
11. The thermoplastic polymer molding composition as claimed in claim 10 which comprises as component (C) the low-molecular oxidized polypropylene in an amount in the range from 0.1 to 2% by weight based on the total amount of the components (A) and (B).
12. The thermoplastic polymeric molding composition as claimed in claim 2 wherein the thermoplastic polymer is selected from the group consisting of polyamide resins, polypropylenes and poly(butylene terephthalates).
13. The thermoplastic polymeric molding composition as claimed in claim 2 wherein the fibrous filler as the component (B-2) is selected from the group consisting of glass fibers, carbon fibers, stainless steel fibers, potassium titanate whiskers and aromatic polyamide fibers.
14. The thermoplastic polymeric molding composition as claimed in claim 2 wherein the water repellent agent is selected from the group consisting of silane coupling agents, titanate coupling agents and silicone fluids.
15. The thermoplastic polymeric molding composition as claimed in claim 2 wherein the water repellent agent is selected from the group consisting of 3-aminopropyl triethoxy silane, N-(2-aminoethyl)-3-aminopropyl trimethoxy silane, isopropyl triisostearoyl titanate, isopropyl tri(N-aminoethyl aminoethyl) titanate, dimethyl silicone fluids and methyl hydrogen polysiloxanes.
16. The thermoplastic polymeric molding composition as claimed in claim 3 wherein the low-molecular weight oxidized polypropylene as the component (C) has an average molecular weight in the range from 1500 to 20000.
17. The thermoplastic polymer molding composition as claimed in claim 16 which comprises as component (C) the low-molecular oxidized polypropylene in an amount in the range from 0.1 to 2% by weight based on the total amount of the components (A) and (B).
18. The thermoplastic polymeric molding composition as claimed in claim 3 wherein the metallic filler as the component (B) is a powder of metallic zinc.
19. The thermoplastic polymeric molding composition as claimed in claim 3 wherein the water repellent agent is selected from the group consisting of silane coupling agents, titanate coupling agents and silicone fluids.
20. The thermoplastic polymeric molding composition as claimed in claim 3 wherein the water repellent agent is selected from the group consisting of 3-aminopropyl triethoxy silane, N-(2-aminoethyl)-3-aminopropyl trimethoxy silane, isopropyl triisostearoyl titanate, isopropyl tri(N-aminoethyl aminoethyl) titanate, dimethyl silicone fluids and methyl hydrogen polysiloxanes.
21. The thermoplastic polymeric molding composition as claimed in claim 4 wherein the low-molecular weight oxidized polypropylene as the component (C) has an average molecular weight in the range from 1500 to 20000.
22. The thermoplastic polymer molding composition as claimed in claim 21 which comprises as component (C) the low-molecular oxidized polypropylene in an amount in the range from 0.1 to 2% by weight based on the total amount of the components (A) and (B).
23. The thermoplastic polymeric molding composition as claimed in claim 4 wherein the metallic filler as the component (B) is a powder of metallic zinc.
24. The thermoplastic polymeric molding composition as claimed in claim 4 wherein the water repellent agent is selected from the group consisting of silane coupling agents, titanate coupling agents and silicone fluids.
25. The thermoplastic polymeric molding composition as claimed in claim 4 wherein the water repellent agent is selected from the group consisting of 3-aminopropyl triethoxy silane, N-(2-aminoethyl)-3-aminopropyl trimethoxy silane, isopropyl triisostearoyl titanate, isopropyl tri(N-aminoethyl aminoethyl) titanate, dimethyl silicone fluids and methyl hydrogen polysiloxanes.
US07/110,129 1986-10-28 1987-10-19 Thermoplastic resin-based molding composition Expired - Fee Related US4891399A (en)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP25468086 1986-10-28
JP61-254680 1986-10-28
JP62156296A JPS63225657A (en) 1986-10-28 1987-06-23 Composite polymer composition
JP62-156296 1987-06-23
JP62-159356 1987-06-26
JP15935687A JPH0764983B2 (en) 1987-06-26 1987-06-26 High specific gravity composite thermoplastic resin composition
JP62166464A JPH0764984B2 (en) 1987-07-03 1987-07-03 Thermoplastic resin composition
JP62-166464 1987-11-09

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